Reversible Addition-fragmentation Chain Transfer Process Research Articles

Tuning the Mechanical Properties of 3D-printed Objects by the RAFT Process: From Chain-Growth to Step-Growth.

Photoinduced 3D printing based on the reversible addition-fragmentation chain transfer (RAFT) process has emerged as a robust method for creating diverse functional materials. However, achieving precise control over the mechanical properties of these printed objects remains a critical challenge for practical application. Here, we demonstrated a RAFT step-growth polymerization of a bifunctional xanthate and bifunctional vinyl acetate. Additionally, we demonstrated photoinduced 3D printing through RAFT step-growth polymerization with a tetrafunctional xanthate and a bifunctional vinyl acetate. By adjusting the molar ratio of the components in the printing resins, we finely tuned the polymerization mechanism from step-growth to chain-growth. This adjustment resulted in a remarkable range of tunable Young's moduli, ranging from 7.6 MPa to 997.1 MPa. Moreover, post-functionalization and polymer welding of the printed objects with varying mechanical properties opens up a promising way to produce tailor-made materials with specific and tunable properties.

Tuning the Mechanical Properties of 3D‐printed Objects by the RAFT Process: From Chain‐Growth to Step‐Growth

AbstractPhotoinduced 3D printing based on the reversible addition‐fragmentation chain transfer (RAFT) process has emerged as a robust method for creating diverse functional materials. However, achieving precise control over the mechanical properties of these printed objects remains a critical challenge for practical application. Here, we demonstrated a RAFT step‐growth polymerization of a bifunctional xanthate and bifunctional vinyl acetate. Additionally, we demonstrated photoinduced 3D printing through RAFT step‐growth polymerization with a tetrafunctional xanthate and a bifunctional vinyl acetate. By adjusting the molar ratio of the components in the printing resins, we finely tuned the polymerization mechanism from step‐growth to chain‐growth. This adjustment resulted in a remarkable range of tunable Young's moduli, ranging from 7.6 MPa to 997.1 MPa. Moreover, post‐functionalization and polymer welding of the printed objects with varying mechanical properties opens up a promising way to produce tailor‐made materials with specific and tunable properties.

Amide-Containing Bottlebrushes via Continuous-Flow Photoiniferter Reversible Addition-Fragmentation Chain Transfer Polymerization: Micellization Behavior.

Herein, a series of ternary amphiphilic amide-containing bottlebrushes were synthesized by photoiniferter (PI-RAFT) polymerization of macromonomers in continuous-flow mode using trithiocarbonate as a chain transfer agent. Visible light-mediated polymerization of macromonomers under mild conditions enabled the preparation of thermoresponsive copolymers with low dispersity and high yields in a very short time, which is not typical for the classical reversible addition-fragmentation chain transfer process. Methoxy oligo(ethylene glycol) methacrylate and alkoxy(C12-C14) oligo(ethylene glycol) methacrylate were used as the basic monomers providing amphiphilic and thermoresponsive properties. The study investigated how modifying comonomers, acrylamide (AAm), methacrylamide (MAAm), and N-methylacrylamide (-MeAAm) affect the features of bottlebrush micelle formation, their critical micelle concentration, and loading capacity for pyrene, a hydrophobic drug model. The results showed that the process is scalable and can produce tens of grams of pure copolymer per day. The unmodified copolymer formed unimolecular micelles at temperatures below the LCST in aqueous solutions, as revealed by DLS and SLS data. The incorporation of AAm, MAAm, and N-MeAAm units resulted in an increase in micelle aggregation numbers. The resulting bottlebrushes formed uni- or bimolecular micelles at extremely low concentrations. These micelles possess a high capacity for loading pyrene, making them a promising choice for targeted drug delivery.

Polymer Functionalization by RAFT Interchange.

Here, we report a simple approach for end group functionalization of linear polymers and graft copolymers via an interchange process of reversible addition-fragmentation chain transfer (RAFT) polymerization chain transfer agents (CTAs). The high functional group tolerance of the RAFT process allows a library of functionalities to be introduced. Moreover, this approach allows multiple functional groups to be installed simultaneously. Furthermore, as an alternative to end group analysis, we report the utility of the supernatant of the reaction mixture to determine the degree of functionalization.

Rapid RAFT Polymerization of Acrylamide with High Conversion.

Rapid RAFT polymerization can significantly improve production efficiency of PAM with designed molecular structure. This study shows that ideal Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization of acrylamide is achieved in dimethyl sulfoxide (DMSO) solution at 70 °C. The key to success is the appropriate choice of both a suitable RAFT chain transfer agent (CTA) and initiating species. It is illustrated that dodecyl trithiodimethyl propionic acid (DMPA) is a suitable trithiocarbonate RAFT CTA and is synthesized more easily than other CTAs. Compared to other RAFT processes of polymers, the reaction system shortens reaction time, enhances conversion, and bears all the characteristics of a controlled radical polymerization. The calculation result shows that high concentrations can reduce high conversions, accelerate the reaction rate, and widen molecular weight distributions slightly. This work proposes an excellent approach for rapid synthesis of PAMs with a restricted molecular weight distribution.

Effects of UV energy on photo-initiated RAFT process of N-vinyl pyrrolidone

Poly (N-vinyl pyrrolidone) was successfully prepared via photo-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization. Methyl (ethoxycarbonothioyl)sulfanyl propionate, used as a chain transfer agent (CTA), undergoes UV-induced photolysis, making it ineffective for the polymerization reaction. To prevent the photolysis of CTA, a photo-initiated RAFT process was carried out using a light emitting diode with narrow-band emission at approximately 410 nm. Photolysis of CTA was effectively prevented, where plots of the ln ([M]0/[M]) vs. time and molecular weight vs. conversion data obtained during the polymerization reaction were linear. Furthermore, it was confirmed that the system was perfectly controlled by light through a light on/off switching test, and the syndiotacticity could be increased by polymerization with fluoroalcohol at low temperature.

3D Printing of Customized Drug Delivery Systems with Controlled Architecture via Reversible Addition‐Fragmentation Chain Transfer Polymerization

3D printing via reversible addition‐fragmentation chain transfer (RAFT) polymerization has been recently developed to expand the scope of 3D printing technologies. A potentially high‐impact but relatively unexplored opportunity that can be provided by RAFT‐mediated 3D printing is a pathway toward personalized medicine through manufacturing bespoke drug delivery systems (DDSs). Herein, 3D printing of drug‐eluting systems with precise geometry, size, drug dosage, and release duration/profiles is reported. This is achieved through engineering a range of 3D models with precise interconnected channel‐pore structure and geometric proportions in architectural patterns. Notably, the application of the RAFT process is crucial in manufacturing materials with highly resolved macroscale features by confining curing to exposure precincts. This approach also allows spatiotemporal control of the drug loading and compositions within different layers of the scaffolds. The ratio between the polyethylene glycol units and the acrylate units in the crosslinkers is found to be a critical factor, with a higher ratio increasing swelling capacity, and thus enhancing the drug release profile, from the drug‐eluting systems. This proof‐of‐concept research demonstrates that RAFT‐mediated 3D printing enables the production of personalized drug delivery materials, providing a pathway to replace the “one‐size‐fits‐all” approach in traditional health care.

Step-growth polymerization by the RAFT process.

Reversible Addition-Fragmentation Chain Transfer (RAFT) step-growth polymerization is an emerging method that synergistically combines the benefits of RAFT polymerization (functional group and user-friendly nature) and step-growth polymerization (versatility of the polymer backbone). This new polymerization method is generally achieved by using bifunctional reagents of monomer and Chain Transfer Agent (CTA), that efficiently yield Single Monomer Unit Insertion (SUMI) adducts under stoichiometrically balanced conditions. This review covers a brief history of the RAFT-SUMI process and its transformation into RAFT step-growth polymerization, followed by a comprehensive discussion of various RAFT step-growth systems. Furthermore, characterizing the molecular weight evolution of step-growth polymerization is elaborated based on the Flory model. Finally, a formula is introduced to describe the efficiency of the RAFT-SUMI process, assuming rapid chain transfer equilibrium. Examples of reported RAFT step-growth and SUMI systems are then categorized based on the driving force.

Mechanoredox Catalysis Enables a Sustainable and Versatile Reversible Addition-Fragmentation Chain Transfer Polymerization Process.

The sustainable synthesis of macromolecules with control over sequence and molar mass remains a challenge in polymer chemistry. By coupling mechanochemistry and electron-transfer processes (i.e., mechanoredox catalysis), an energy-conscious controlled radical polymerization methodology is realized. This work explores an efficient mechanoredox reversible addition-fragmentation chain transfer (RAFT) polymerization process using mechanical stimuli by implementing piezoelectric barium titanate and a diaryliodonium initiator with minimal solvent usage. This mechanoredox RAFT process demonstrates exquisite control over poly(meth)acrylate dispersity and chain length while also showcasing an alternative to the solution-state synthesis of semifluorinated polymers that typically utilize exotic solvents and/or reagents. This chemistry will find utility in the sustainable development of materials across the energy, biomedical, and engineering communities.

Mechanoredox Catalysis Enables a Sustainable and Versatile Reversible Addition‐Fragmentation Chain Transfer Polymerization Process

AbstractThe sustainable synthesis of macromolecules with control over sequence and molar mass remains a challenge in polymer chemistry. By coupling mechanochemistry and electron‐transfer processes (i.e., mechanoredox catalysis), an energy‐conscious controlled radical polymerization methodology is realized. This work explores an efficient mechanoredox reversible addition‐fragmentation chain transfer (RAFT) polymerization process using mechanical stimuli by implementing piezoelectric barium titanate and a diaryliodonium initiator with minimal solvent usage. This mechanoredox RAFT process demonstrates exquisite control over poly(meth)acrylate dispersity and chain length while also showcasing an alternative to the solution‐state synthesis of semifluorinated polymers that typically utilize exotic solvents and/or reagents. This chemistry will find utility in the sustainable development of materials across the energy, biomedical, and engineering communities.

Morphology Control via RAFT Emulsion Polymerization-Induced Self-Assembly: Systematic Investigation of Core-Forming Blocks.

Polymerization-induced self-assembly (PISA) is a useful formulation for readily obtaining nanoparticles from block copolymers in situ. Reversible addition–fragmentation chain-transfer (RAFT) emulsion polymerization is utilized as one of the PISA formulations. Various factors have so far been investigated for obtaining nonspherical particles via RAFT emulsion polymerization, such as the steric structure of the shell, the glass-transition temperature (Tg) of the core-forming block, and the water solubility of the core-forming monomer. This study focuses on core-forming blocks without changing the structure of the shell-forming block. In particular, we elucidate the balance between Tg for the core-forming block and the water solubility of the core monomer. A series of alkyl methacrylates, such as methyl methacrylate (MMA), ethyl methacrylate (EMA), and n-propyl methacrylate (PrMA), are emulsion-polymerized in the presence of a poly[poly(ethylene glycol) methyl ether methacrylate] (PPEGMA) macromolecular chain-transfer agent via the RAFT process. The resulting in situ morphology changes to form shapes such as spheres, worms (toroids), and vesicles are systematically investigated. The properties of the core that determine whether a morphological change occurs from spheres are (i) the solubility of the core-forming monomer in water, (ii) the relationship between Tg for the core-forming block and the polymerization temperature, and (iii) the hydrophobic core volume, which changes the packing parameter. These factors allow prediction of the block copolymer morphology produced during RAFT emulsion polymerization of other methacrylates such as n-butyl methacrylate (BuMA), tetrahydrofurfuryl methacrylate (THFMA) with physical properties of the homopolymer (poly(tetrahydrofurfuryl methacrylate) (PTHFMA)) between those for poly(MMA) (PMMA) and PBuMA, and 1-adamantyl methacrylate (ADMA) with low monomer solubility in water and high Tg of the homopolymer (PADMA).

Dual Function of β-Hydroxy Dithiocinnamic Esters: RAFT Agent and Ligand for Metal Complexation.

The reversible addition-fragmentation chain-transfer (RAFT) process has become a versatile tool for the preparation of defined polymers tolerating a large variety of functional groups. Several dithioesters, trithiocarbonates, xanthates, or dithiocarbamates have been developed as effective chain transfer agents (CTAs), but only a few examples have been reported, where the resulting end groups are directly considered for a secondary use besides controlling the polymerization. Herein, it is demonstrated that β-hydroxy dithiocinnamic esters represent a hitherto overlooked class of materials, which are originally designed for the complexation of transition metals but may as well act as reversible CTAs. Modified with a suitable leaving group (R-group), these vinyl conjugated dithioesters indeed provide reasonable control over the polymerization of acrylates, acrylamides, or styrene via the RAFT process. Kinetic studies reveal linear evolutions of molar mass with conversion, while different substituents on the aromatic unit has only a minor influence. Block extensions prove the livingness of the polymer chains, although extended polymerization times may lead to side reactions. The resulting dithiocinnamic ester end groups are still able to form complexes with platinum, which verifies that the structural integrity of the end group is maintained. These findings open a versatile new route to tailor-made polymer-bound metal complexes.

Synthesis and Study of Thermoresponsive Amphiphilic Copolymers via RAFT Polymerization.

Synthesis and study of well-defined thermoresponsive amphiphilic copolymers with various compositions were reported. Kinetics of the reversible addition-fragmentation chain transfer (RAFT) (co)polymerization of styrene (St) and oligo(ethylene glycol) methyl ether methacrylate (PEO5MEMA) was studied by size exclusion chromatography (SEC) and 1H NMR spectroscopy, which allows calculating not only (co)polymerization parameters but also gives valuable information on RAFT (co)polymerization kinetics, process control, and chain propagation. Molecular weight Mn and dispersity Đ of the copolymers were determined by SEC with triple detection. The detailed investigation of styrene and PEO5MEMA (co)polymerization showed that both monomers prefer cross-polymerization due to their low reactivity ratios (r1 < 1, r2 < 1); therefore, the distribution of monomeric units across the copolymer chain of p(St-co-PEO5MEMA) with various compositions is almost ideally statistical or azeotropic. The thermoresponsive properties of p(St-co-PEO5MEMA) copolymers in aqueous solutions as a function of different hydrophilic/hydrophobic substituent ratios were evaluated by measuring the changes in hydrodynamic parameters under applied temperature using the dynamic light scattering method (DLS).

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.

Construction of hypercrosslinked polymers with styrene-based copolymer precursor for adsorption of rare earth elements

Adsorption and separation of rare earth elements (REEs) are of significant importance due to their unique properties and low supply of these elements. Porous hypercrosslinked polymers (HCPs) are currently an important category of polymer adsorbents and attracting great interest because of their merits including high surface area, moderate synthetic conditions and various building blocks. Herein, for the first time, we constructed HCPs with copolymers precursors and applied to the adsorption of REEs. Styrene (S) and glycidyl methacrylate-iminodiacetic acid (GMA-IDA) were polymerized by a facile reversible addition-fragmentation chain transfer process, and GMA-IDA-co-PS copolymers were employed as precursors to construct HCPs. The adsorption behavior of REEs was investigated in detail with Tb3+ as a representative. The separation of light, medium and heavy REEs was also studied. It is the first attempt that copolymers were employed to the preparation of HCPs and used in the area of REEs adsorption, which can serve as a foundation for further design and application of various HCPs in the field of adsorption.

Photo-Iniferter RAFT Polymerization.

Light-mediated polymerization techniques offer distinct advantages over polymerization reactions fueled by thermal energy, such as high spatial and temporal control as well as the possibility to work under mild reaction conditions. Reversible addition-fragmentation chain-transfer (RAFT) polymerization is a highly versatile radical polymerization method that can be utilized to control a variety of monomers and produce a vast number of complex macromolecular structures. The use of light to drive a RAFT-polymerization is possible via multiple routes. Besides the use of photo-initiators, or photo-catalysts, the direct activation of the chain transfer agent controlling the RAFT process in a photo-iniferter (PI) process is an elegant way to initiate and control polymerization reactions. Within this review, PI-RAFT polymerization and its advantages over the conventional RAFT process are discussed in detail.

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.

Enhanced Heat Resistance and Adhesive Strength of Styrene-Acrylic Triblock Copolymer Elastomers by Incorporating Acrylic Acid.

Herein, we present an industrially applicable strategy to enhance the heat resistance and adhesive properties of ABA triblock copolymer-based elastomers composed of styrene (St) and n-butyl acrylate (nBA) by incorporating acrylic acid (AA) at different segments. Three types of triblock copolymers, namely, poly(St-r-AA)-b-poly(nBA)-b-poly(St-r-AA), poly(St)-b-poly(nBA-r-AA)-b-poly(St), and poly(St)-b-poly(nBA)-b-poly(St), were synthesized by reversible addition–fragmentation chain-transfer (RAFT) polymerization. Large-scale RAFT polymerization afforded industrially applicable AA-containing triblock copolymers with moderate molecular weights and predetermined comonomer compositions (St/nBA/AA = 15/83/2–24/73/3, number-average molecular weight (Mn) = 30,000–110,000, and resulting product > 200 g). The heat resistance and pressure-sensitive adhesive properties of the triblock copolymers were evaluated. Among them, poly(St-r-AA)-b-poly(nBA)-b-poly(St-r-AA), having poly(nBA) as the middle soft segment and poly(St-r-AA) as hard segments at both ends, exhibited excellent heat creep resistance and increased adhesiveness to stainless steel. The feasibility to manipulate the heat resistance and adhesive properties by incorporating AA units into hard and soft segments, in addition to the ease of operation, high block efficiency, and metal-free nature owing to the RAFT process, is highly beneficial for practical applications of these copolymers.

A Facile Preparation of Mussel-Inspired Poly(dopamine phosphonate-co-PEGMA)s via a One-Pot Multicomponent Polymerization System.

Mussel-inspired polymers attract much research interest due to their potential as effective adhesives. In this work, a new kind of mussel-inspired polymer, poly(dopamine phosphonate-co-PEGMA), is prepared via a one-pot multicomponent polymerization system. The multicomponent polymerization system refers to a combination of multicomponent Kabachnik-Fields (KF) reaction and reversible addition-fragmentation chain transfer (RAFT) polymerization system. Reactants are converted to dopamine phosphonate monomers in situ through the KF reaction and polymerized simultaneously along with poly(ethylene glycol methyl ether) methacrylate (PEGMA) co-monomers by the RAFT process in a one-pot operation. Target polymers with dopamine phosphonate as side groups and well-defined polymer structures are thus facilely and successfully prepared. Afterwards, a series of polymers with various ratios of dopamine phosphonates as well as the crosslinked polymer analogues are prepared. Benefiting from the dopamine phosphonate side groups, aqueous solutions of those polymers show potential as effective adhesives in both dry and wet conditions, and their adhesive strengths are highly related to ratios of dopamine phosphonates in the polymers. Those polymers are non-cytotoxic and show strong bonding affinities on various substrates including metals, polymers, and bovine bones, suggesting their potential as environmentally friendly general adhesives in broad areas.

Asymmetrically Substituted Poly(diitaconates) Obtained by Reversible Addition‐Fragmentation Chain Transfer (RAFT) Polymerization: Synthesis, Copolymerization Parameters, and Antimicrobial Activity

AbstractAsymmetrically substituted poly(diitaconate) copolymers are synthesized from 1‐((N‐tert‐butoxycarbonyl)‐2‐aminoethyl)‐4‐propyl diitaconate (PrIA) and different comonomers (N,N‐dimethyl‐acrylamide, DMAA; acrylic acid; or ((N‐tert‐butoxycarbonyl)‐2‐aminoethyl)methacrylate) by reversible addition–fragmentation chain transfer polymerization (RAFT). The RAFT copolymerization parameters of PrIA and DMAA are rDMAA = 0.49 and rPrIA = 0.17, compared to rDMAA = 0.52 and rPrIA = 0.54 obtained by free radical copolymerization (FRP). Thus, the RAFT process has a stronger trend to alternating polymerization than the FRP process. The polydispersity index of the RAFT copolymers is around 1.2–1.8, compared to 2.8–2.9 for the corresponding FRP copolymers. After removal of the tert‐butoxycarbonyl protective groups, antimicrobially active synthetic mimics of antimicrobial peptides are obtained. The thus activated poly(PrIA‐co‐DMAA) copolymers (repeat unit ratio 1:1) have an increasing activity against Escherichia coli and Staphylococcus aureus with increasing molar mass. The RAFT copolymers are slightly more active and less toxic than comparable FRP polymers, leading to a higher selectivity for bacteria over mammalian cells. Higher molar fractions of PrIA in poly(PrIA‐co‐DMAA) copolymers (up to 80 mol%) do not increase their antimicrobial activity; reduction of the BuIA content in poly(BuIA‐DMAA) (down to 10 mol%) leads to a loss of activity against both E. coli and S. aureus.