Cationic Reversible Addition-fragmentation Chain Transfer Research Articles

Orthogonal Radical and Cationic Single-Unit Monomer Insertions for Engineering Polymer Architectures.

The single-unit monomer insertion (SUMI), derived from living/controlled polymerization, can be directly functionalized at the end or within the chain of polymers prepared by living/controlled polymerization, offering potential applications in the preparation of polymers with complex architectures. Many scenarios demand the simultaneous incorporation of monomers suitable for different polymerization methods into complex polymers. Therefore, it becomes imperative to utilize SUMI technologies with diverse mechanisms, especially those that are compatible with each other. Here, we reported the orthogonal SUMI technique, seamlessly combining radical and cationic SUMI approaches. Through the careful optimization of monomer and chain transfer agent pairs and adjustments to reaction conditions, we can efficiently execute both radical and cationic SUMI processes in one pot without mutual interference. The utilization of orthogonal SUMI pairs facilitates the integration of radical and cationic reversible addition-fragmentation chain transfer (RAFT) polymerization in various configurations. This flexibility enables the synthesis of diblock, triblock, and star polymers that incorporate both cationically and radically polymerizable monomers. Moreover, we have successfully implemented a mixing mechanism of free radicals and cations in RAFT step-growth polymerization, resulting in the creation of a side-chain sequence-controlled polymer brushes.

Fast Living 3D Printing via Free Radical Promoted Cationic RAFT Polymerization.

The application of reversible deactivation radical polymerization techniques in 3D printing is emerging as a powerful method to build "living" polymer networks, which can be easily postmodified with various functionalities. However, the building speed of these systems is still limited compared to commercial systems. Herein, a digital light processing (DLP)-based 3D printing system via photoinduced free radical-promoted cationic reversible addition-fragmentation chain transfer polymerization of vinyl ethers, which can build "living" objects by a commercial DLP 3D printer at a relatively fast building speed (12.99cm h-1 ), is reported. The polymerization behavior and printing conditions are studied in detail. The livingness of the printed objects is demonstrated by spatially controlled postmodification with a fluorescent monomer.

Scalable, Green Chain Transfer Agent for Cationic RAFT Polymerizations

Comprehensive SummaryCationic polymerizations of vinyl ethers have gained recent attention due to their ability to produce robust, biorenewable materials. These developments have been largely enabled by the advent of cationic reversible addition−fragmentation chain‐transfer (RAFT) polymerization; however, the scalability and sustainability of this method are hindered by current chain‐transfer agents (CTAs), which exist as viscous, colored oils requiring complex syntheses and solvent‐intensive purification. Herein, we produce a solid, colorless CTA through a green synthetic route in 83% yield on a 50‐gram scale. We investigate the utility of this CTA in chemical, electrochemical, photochemical, and acid‐initiated methods, revealing that it achieves efficient polymerization with excellent control over molecular weight, low dispersity values, high chain end fidelity, and temporal control in cationic RAFT polymerizations.

Monophosphoniums as Effective Photoredox Organocatalysts for Visible Light-Regulated Cationic RAFT Polymerization.

Visible light-regulated metal-free polymerizations have attracted considerable attention for macromolecular syntheses in recent years. However, few organic photocatalysts show high efficiency and strict photocontrol in cationic polymerizations. Herein, we introduce monophosphonium-doped polycyclic arenes as an organic photocatalyst, which features the high tunability, broad redox window, long excited state lifetime, and excellent temporal control in the cationic reversible addition-fragmentation chain transfer polymerization of vinyl ethers. A correlation of the catalytic performance and the photophysical and electrochemical properties of photocatalysts is also discussed.

Photoinduced 3D Printing through a Combination of Cationic and Radical RAFT Polymerization

Photopolymerization-based three-dimensional (3D) printing techniques have been widely utilized to fabricate polymeric materials with complex architectures. The application of reversible deactivation radical polymerization (RDRP) in 3D printing is emerging as a powerful tool to introduce various postprinting abilities but is still at an early stage. Here, a photoinduced free radical-promoted cationic reversible addition–fragmentation chain transfer (RAFT) polymerization method was developed, utilizing the direct photolysis of the RAFT agent as a radical source, which was further combined with photo-iniferter RAFT polymerization to prepare polymer networks. The polymerization mechanism was studied by model polymerization using monofunctional monomers. The effects of each component on the properties of the final materials and polymerization behavior of the cross-linking systems were studied in detail. This method was successfully applied in a digital light processing (DLP) technique-based commercial 3D printer. Finally, polymer welding of the printed objects through both cationic and radical RAFT chain extension was realized, expanding avenues of postprinting and future applications in various fields.

Organocatalytic, Stereoselective, Cationic Reversible Addition-Fragmentation Chain-Transfer Polymerization of Vinyl Ethers.

Tacticity is a crucial factor affecting the properties of synthetic polymer materials. Here, we introduce a type of chiral organic Brønsted acid catalyst, 1,1'-bi-2-naphthol-derived N,N'-bis(triflyl)phosphoramidimidates (PADIs), for the cationic polymerization of vinyl ethers, which enables the development of the first organocatalytic, highly stereoselective, cationic reversible addition-fragmentation chain-transfer (RAFT) polymerization of vinyl ethers with a trithiocarbonate chain-transfer agent. This metal-free RAFT process could afford isotactic poly(vinyl ethers) with high stereoselectivity, controllable molecular mass, and narrow dispersity at low catalyst loadings (as low as 200 ppm). Moreover, the trithiocarbonate chain-end allows for chain extension to synthesize diblock copolymers comprising an isotactic poly(vinyl ether) block, by a mechanistic switching from stereoselective cationic RAFT polymerization to visible-light-regulated cationic and radical RAFT polymerization.

Photoinduced Free Radical Promoted Cationic RAFT Polymerization toward “Living” 3D Printing

Three-dimensional (3D) printing utilizing controlled polymerization systems is emerging as a powerful approach to fabricate "living" objects, which can be further modified with various functionalities. Here, we report photoinduced free radical-promoted cationic reversible addition-fragmentation chain transfer (RAFT) polymerization under broad wavelengths from ultraviolet (UV) to near-infrared (NIR) light. A commercially available iron catalyst, cyclopentadienyl iron dicarbonyl dimer (Fe2(Cp)2(CO)4), was used as the photocatalyst, and several diphenyliodonium salts were examined as oxidants. Various poly(vinyl ether)s with controlled molecular weights and a narrow dispersity (1.06-1.32) were prepared through this method. Relatively high chain-end fidelity can be observed and has been demonstrated by successful chain-extension experiments. In addition, benefiting from the penetrating ability of NIR light, 3D objects with different thicknesses were achieved by employing stereolithography-based 3D printing techniques. Furthermore, the postfunctionalization of these 3D printed objects with fluorescent monomers provides a facile method to build 3D objects with complex functionality and potential applications in anticounterfeiting materials.

Recent Advances in Living Cationic Polymerization with Emerging Initiation/Controlling Systems.

While the conventional living cationic polymerization (LCP) provided opportunities to synthesizing well-defined polymers with predetermined molecular weights, desirable chemical structures and narrow dispersity, it is still important to continuously innovate new synthetic methods to meet the increasing requirements in advanced material engineering. Consequently, a variety of novel initiation/controlling systems have be demonstrated recently, which have enabled LCP with spatiotemporal control, broadened scopes of monomers and terminals, more user-friendly operations and reaction conditions, as well as improved thermomechanical properties for obtained polymers. In this work, recent advances in LCP is summarized with emerging initiation/controlling systems, including chemical-initiated/controlled cationic reversible addition-fragmentation chain transfer (RAFT) polymerization, photoinitiated/controlled LCP, electrochemical-controlled LCP, thionyl/selenium halide-initiated LCP, organic acid-assisted LCP, and stereoselective LCP. It is hoped that this summary will provide useful knowledge to people in related fields and stimulate new ideas to promote the development and application of LCP in both academia and industry.

Manganese-Catalyzed Batch and Continuous Flow Cationic RAFT Polymerization Induced by Visible Light.

We present a robust manganese-catalyzed cationic reversible addition-fragmentation chain transfer (RAFT) polymerization induced by visible light. Well-defined poly(vinyl ether)s with controlled molecular weight and molecular weight distributions (MWDs) can be conveniently prepared at room temperature without monomer purification. The commercially available manganese carbonyl bromide is used as the photocatalyst for cationic RAFT polymerization. Moreover, this method has been further applied in both batch and continuous flow systems, providing a visible light induced flow cationic polymerization under mild conditions.

Stereospecific cationic RAFT polymerization of bulky vinyl ethers and stereoblock poly(vinyl alcohol) via mechanistic transformation to radical RAFT polymerization of vinyl acetate

The simultaneous control of molecular weight and tacticity in cationic polymerization remains challenging. Here, we propose a new approach for stereospecific living cationic polymerization by combining cationic reversible addition-fragmentation chain transfer (RAFT) polymerization with thiocarbonylthio compounds and stereospecific cationic polymerization of bulky vinyl ethers with Lewis acid catalysts. In this combined system, the molecular weight was controlled by the RAFT process between the growing cationic and dormant dithiocarbamate chain ends, whereas the tacticity was controlled by stereospecific propagation based on the steric hindrance of bulky side groups and counteranions derived from the Lewis acid catalysts. Herein, we demonstrate the availability of this approach in the cationic polymerization of various bulky vinyl ethers, such as tert‑butyl, benzyl, trimethylsilyl, and tert‑butyldimethylsilyl vinyl ether, using dithiocarbamates and BF3•OEt2 or EtAlCl2 in toluene at –78 °C. Isotactic-rich poly(vinyl ether)s with controlled molecular weights and dithiocarbamate chain-end groups were obtained from a series of bulky vinyl ethers and were converted into molecular-weight-controlled isotactic poly(vinyl alcohol) (mm ≥ 70%) with a high melting temperature (Tm ~ 230 °C). Furthermore, isotactic-b-atactic stereoblock PVA (mm/mr/rr = 75/25/5 and 23/48/29, Tm ~ 210 °C) was synthesized by mechanistic transformation from the stereospecific cationic RAFT polymerization of trimethylsilyl vinyl ether into the radical RAFT polymerization of vinyl acetate using diphenyl dithiocarbamate as the common RAFT agent followed by simultaneous deprotection of the silyl and acetyl groups.

Near-Infrared, Light-Induced Cationic and Radical RAFT Polymerization Catalyzed by Iron Complex.

A near-infrared (NIR) light induced controlled cationic polymerization is presented here. The halide abstraction reaction between the cyclopentadienyl iron dicarbonyl dimer (Fe2(Cp)2(CO)4) and an organic halide is utilized to generate initial radicals or cations under mild conditions, which can be further combined with both radical and cationic reversible addition-fragmentation chain transfer (RAFT) polymerization. Well-defined poly(vinyl ether)s and polyacrylates are prepared successfully under NIR light by this method. The excellent penetration ability of NIR light through thick barriers has been verified by polymerization in the presence of an A4 paper. In addition, iron-based radical polymerization has been used for three-dimensional (3D) printing to fabricate materials with different thicknesses.

Manganese carbonyl induced cationic reversible addition–fragmentation chain transfer (C-RAFT) polymerization under visible light

Vinyl ethers were polymerized by C-RAFT polymerization on the basis of halide abstraction reaction of manganese carbonyl and organic halide.

Diversifying Cationic RAFT Polymerization with Various Counteranions: Generation of Cationic Species from Organic Halides and Various Metal Salts.

A combination of hydrogen chloride adduct of isobutyl vinyl ether (IBVE-HCl) and various metal salts (AgOTf, AgPF6, AgSbF6, NaBArF (BArF: [3,5-(CF3)2Ph]4B)) efficiently generated initiating cationic species with different low, weakly, or non-nucleophilic counteranions (OTf-, PF6-, SbF6-, BArF-) and induced a cationic reversible-addition-fragmentation chain-transfer (RAFT) or degenerative chain-transfer (DT) polymerization of IBVE, ethyl vinyl ether, p-methoxystyrene, and α-methylstyrene (αMS) in the presence of appropriate thiocarbonylthio compounds or thioethers as reversible chain-transfer agents. The polymerization behaviors in terms of polymerization rate, polymer molecular weight, terminal structure, and stereochemistry were affected by the counteranions, whereas the molecular weight control was achieved by appropriate RAFT or DT agents for all of these counteranions. With a weakly or noncoordinating BArF anion and a trithiocarbonate, a nearly atactic poly(IBVE) with a narrow molecular weight distribution (Mw/Mn < 1.1) was obtained. When using nonoxoanions, such as SbF6-, PF6-, and BArF-, in the presence of thioethers, controlled cationic polymerization of αMS was achieved while frequent irreversible β-proton elimination occurred using TfO-. Thus, this method widens the scope of living or controlled cationic polymerizations with various counteranions.

Tailor-Made Fluorinated Copolymer/Clay Nanocomposite by Cationic RAFT Assisted Pickering Miniemulsion Polymerization

Fluorinated polymers in emulsion find enormous applications in hydrophobic surface coating. Currently, lots of efforts are being made to develop specialty polymer emulsions which are free from surfactants. This investigation reports the preparation of a fluorinated copolymer via Pickering miniemulsion polymerization. In this case, 2,2,3,3,3-pentafluoropropyl acrylate (PFPA), methyl methacrylate (MMA), and n-butyl acrylate (nBA) were copolymerized in miniemulsion using Laponite-RDS as the stabilizer. The copolymerization was carried out via reversible addition-fragmentation chain transfer (RAFT) process. Here, a cationic RAFT agent, S-1-dodecyl-S'-(methylbenzyltriethylammonium bromide) trithiocarbonate (DMTTC), was used to promote polymer-Laponite interaction by means of ionic attraction. The polymerization was much faster when Laponite content was 30 wt % or above with 1.2 wt % RAFT agent. The stability of the miniemulsion in terms of zeta potential was found to be dependent on the amount of both Laponite and RAFT agent. The miniemulsion had particle sizes in the range of 200-300 nm. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) analyses showed the formation of Laponite armored spherical copolymer particles. The fluorinated copolymer films had improved surface properties because of polymer-Laponite interaction.

Self-assembled gold coating enhances X-ray imaging of alginate microcapsules.

Therapeutic biomolecules produced from cells encapsulated within alginate microcapsules (MCs) offer a potential treatment for a number of diseases. However the fate of such MCs once implanted into the body is difficult to establish. Labelling the MCs with medical imaging contrast agents may aid their detection and give researchers the ability to track them over time thus aiding the development of such cellular therapies. Here we report the preparation of MCs with a self-assembled gold nanoparticle (AuNPs) coating which results in distinctive contrast and enables them to be readily identified using a conventional small animal X-ray micro-CT scanner. Cationic Reversible Addition-Fragmentation chain Transfer (RAFT) homopolymer modified AuNPs (PAuNPs) were coated onto the surface of negatively charged alginate MCs resulting in hybrids which possessed low cytotoxicity and high mechanical stability in vitro. As a result of their high localized Au concentration, the hybrid MCs exhibited a distinctive bright circular ring even with a low X-ray dose and rapid scanning in post-mortem imaging experiments facilitating their positive identification and potentially enabling them to be used for in vivo tracking experiments over multiple time-points.

Cationic RAFT Polymerization Using ppm Concentrations of Organic Acid

AbstractA metal‐free, cationic, reversible addition–fragmentation chain‐transfer (RAFT) polymerization was proposed and realized. A series of thiocarbonylthio compounds were used in the presence of a small amount of triflic acid for isobutyl vinyl ether to give polymers with controlled molecular weight of up to 1×105 and narrow molecular‐weight distributions (Mw/Mn&lt;1.1). This “living” or controlled cationic polymerization is applicable to various electron‐rich monomers including vinyl ethers, p‐methoxystyrene, and even p‐hydroxystyrene that possesses an unprotected phenol group. A transformation from cationic to radical RAFT polymerization enables the synthesis of block copolymers between cationically and radically polymerizable monomers, such as vinyl ether and vinyl acetate or methyl acrylate.

Cationic RAFT polymerization using ppm concentrations of organic acid.

A metal-free, cationic, reversible addition-fragmentation chain-transfer (RAFT) polymerization was proposed and realized. A series of thiocarbonylthio compounds were used in the presence of a small amount of triflic acid for isobutyl vinyl ether to give polymers with controlled molecular weight of up to 1×10(5) and narrow molecular-weight distributions (Mw /Mn <1.1). This "living" or controlled cationic polymerization is applicable to various electron-rich monomers including vinyl ethers, p-methoxystyrene, and even p-hydroxystyrene that possesses an unprotected phenol group. A transformation from cationic to radical RAFT polymerization enables the synthesis of block copolymers between cationically and radically polymerizable monomers, such as vinyl ether and vinyl acetate or methyl acrylate.

Control of the anisotropic morphology of latex nanocomposites containing single montmorillonite clay particles prepared by conventional and reversible addition‐fragmentation chain transfer based emulsion polymerization

AbstractSingle montmorillonite platelets have been successfully encapsulated by polymer through both a conventional and a reversible addition‐fragmentation chain transfer (RAFT) based emulsion polymerization. For both synthetic methods, the encapsulation process basically consisted of three steps: (i) adsorption of cationic RAFT copolymers (RAFT approach) or surfactant (conventional approach); (ii) high shear dispersion of the stabilized clay in aqueous solutions; (iii) starved‐feed addition of monomers starting the polymerization. In the conventional approach, the morphology of the latex/clay nanocomposites was close to the dumbbell shapes previously reported and did not depend on the presence of organic modifier as evidenced by cryotransmission electron microscopy and scanning electron microscopy. In the RAFT approach a completely different morphology was obtained which has been coined the cornflake morphology. With these two new approaches we can control the orientation of the clay platelets inside the latex particles which in turn can control the orientation of the clay platelets in a film. A perspective on possible applications of these different morphologies is given, e.g. their use in high barrier coatings. Copyright © 2012 Society of Chemical Industry