Reversible Deactivation Radical Polymerization Research Articles

Progress and Perspectives Beyond Traditional RAFT Polymerization.

The development of advanced materials based on well‐defined polymeric architectures is proving to be a highly prosperous research direction across both industry and academia. Controlled radical polymerization techniques are receiving unprecedented attention, with reversible‐deactivation chain growth procedures now routinely leveraged to prepare exquisitely precise polymer products. Reversible addition‐fragmentation chain transfer (RAFT) polymerization is a powerful protocol within this domain, where the unique chemistry of thiocarbonylthio (TCT) compounds can be harnessed to control radical chain growth of vinyl polymers. With the intense recent focus on RAFT, new strategies for initiation and external control have emerged that are paving the way for preparing well‐defined polymers for demanding applications. In this work, the cutting‐edge innovations in RAFT that are opening up this technique to a broader suite of materials researchers are explored. Emerging strategies for activating TCTs are surveyed, which are providing access into traditionally challenging environments for reversible‐deactivation radical polymerization. The latest advances and future perspectives in applying RAFT‐derived polymers are also shared, with the goal to convey the rich potential of RAFT for an ever‐expanding range of high‐performance applications.

Thermally Assisted Fluorescent Polymers: Polycyclic Aromatic Materials for High Color Purity and White-Light Emission.

Thermally activated delayed fluorescence (TADF) sensitization of fluorescence is a promising strategy to improve the color purity and operational lifetime of conventional TADF organic light-emitting diodes (OLEDs). Here, we propose a new design strategy for TADF-sensitized fluorescence based on acrylic polymers with a pendant energy-harvesting host, a TADF sensitizer, and fluorescent emitter monomers. Fluorescent emitters were rationally designed from a series of homologous polycyclic aromatic amines, resulting in efficient and color-pure polymeric fluorophores capable of harvesting both singlet and triplet excitons. Macromolecular analogues of blue, green, and yellow fourth-generation OLED emissive layers were prepared in a facile manner by Cu(0) reversible deactivation radical polymerization, with emission quantum yields up to 0.83 in air and narrow emission bands with full width at half-maximum as low as 57 nm. White-light emission can easily be achieved by enforcing incomplete energy transfer between a deep blue TADF sensitizer and yellow fluorophore to yield a single white-emissive polymer with CIE coordinates (0.33, 0.39) and quantum yield 0.77. Energy transfer to the fluorescent emitters occurs at rates of 1-4 × 108 s-1, significantly faster than deactivation caused by internal conversion or intersystem crossing. Rapid energy transfer facilitates high triplet exciton utilization and efficient sensitized emission, even when TADF emitters with a low quantum yield are used as photosensitizers. Our results indicate that a broad library of untapped polymers exhibiting efficient TADF-sensitized fluorescence should be readily accessible from known TADF materials, including many monomers previously thought unsuitable for use in OLEDs.

Multi-Arm Star-Shaped Glycopolymers with Precisely Controlled Core Size and Arm Length.

Star-shaped glycopolymers provide very high binding activities toward lectins. However, a straightforward synthesis method for the preparation of multi-arm glycopolymers in a one-pot approach has been challenging. Herein, we report a rapid synthesis of well-defined multi-arm glycopolymers via Cu(0)-mediated reversible deactivation radical polymerization in aqueous media. d-Mannose acrylamide has been homo- and copolymerized with NIPAM to provide linear arms and then core cross-linked with a bisacrylamide monomer. Thus, the arm length and core size of multi-arm glycopolymers were tuned. Moreover, the stability of multi-arm glycopolymers was investigated, and degradation reactions under acidic or basic conditions were observed. The binding activities of the obtained multi-arm glycopolymers with mannose-specific human lectins, DC-SIGN and MBL, were investigated via surface plasmon resonance spectroscopy. Finally, the encapsulation ability of multi-arm glycopolymers was examined using DHA and Saquinavir below and above the lower critical solution temperature (LCST) of P(NIPAM).

Effect of Arm Number and Length of Star-Shaped Glycopolymers on Binding to Dendritic and Langerhans Cell Lectins.

Many cell types in Nature are covered by glycans with a sugar shell on their surface. Synthetic glycopolymer-based materials can mimic these glycans in terms of their variety of biological processes, such as cell growth regulation, adhesion, inflammation by bacteria and viruses, and immune responses. However, the complexity of glycans is still very challenging to be mimicked completely to obtain specific and selective binding ability. Therefore, in this study we aimed to understand how the complexity in the sense of the effect of number of arms and lengths in star-shaped glycopolymers affect the binding activity with different lectins. The Cu-mediated reversible deactivation radical polymerization (Cu-RDRP) technique was employed for the synthesis of mannose containing star-shaped glycopolymers with varying arm number and length. Two sets of star-shaped glycopolymers with on average 1, 3, 7, 8, and 15 arms were successfully synthesized and characterized via 1H NMR, GPC, and DLS. The first set of glycopolymers (Set S1) encompasses 5 star-shaped glycopolymers with a different amount of arms per macromolecule but with equal arm length, whereas in the second set of 5 glycopolymers (Set S2), the amount of sugars per macromolecule was kept constant to obtain glycopolymers with similar glycovalency but in different configuration. Both glycopolymer sets were subsequently evaluated for their lectin-binding affinity toward a series of both newly and previously studied C-type mannose specific lectins present on dendritic and Langerhans cells. Briefly, while Set S1 glycopolymers with the same arm length and different molecular weight showed considerably different biological activities, Set S2 glycopolymers with different arm lengths and the same molecular weight displayed very similar binding abilities, which can indicate that multivalency can be more important than structure complexity to improve the binding behavior of glycopolymers.

Assembly of silica nanoparticles based on stimuli-responsive covalent bonding between glycopolymers and poly(phenylboronic acid)s

Covalent bonding between boronic acid and cis-diols is widely used to prepare stimuli-responsive nano materials. Herein, we report a kind of extremely rapid formation of boronate esters between glycopolymers and poly(phenylboronic acid)s for the assembly of silica nanoparticles. High-density poly(glycidyl methacrylate) brushes are first immobilized onto the surface of silica nanoparticles by surface initiated Cu(0) mediated reversible deactivation radical polymerization (SI-Cu(0)-RDRP). Subsequent post-polymerization modifications via click chemistry facilely fabricate the polymer scaffolds with pendent saccharides or phenylboronic acid (PBA) units. The rapid formation of boronate esters between glycopolymer and poly(PBA) induces further self-assembly and fast aggregation of nanoparticles. The sugar-containing boronate esters could survive under high temperature, excess monosaccharides and extreme pH. Hyper-cross-linked glycopolymer networks with tuned porous properties are prepared after etching of silica templates by hydrofluoric acid.

The Competition of Termination and Shielding to Evaluate the Success of Surface-Initiated Reversible Deactivation Radical Polymerization.

One of the challenges for brush synthesis for advanced bioinspired applications using surface-initiated reversible deactivation radical polymerization (SI-RDRP) is the understanding of the relevance of confinement on the reaction probabilities and specifically the role of termination reactions. The present work puts forward a new matrix-based kinetic Monte Carlo platform with an implicit reaction scheme capable of evaluating the growth pattern of individual free and tethered chains in three-dimensional format during SI-RDRP. For illustration purposes, emphasis is on normal SI-atom transfer radical polymerization, introducing concepts such as the apparent livingness and the molecular height distribution (MHD). The former is determined based on the combination of the disturbing impact of termination (related to conventional livingness) and shielding of deactivated species (additional correction due to hindrance), and the latter allows structure-property relationships to be identified, starting at the molecular level in view of future brush characterization. It is shown that under well-defined SI-RDRP conditions the contribution of (shorter) hindered dormant chains is relevant and more pronounced for higher average initiator coverages, despite the fraction of dead chains being less. A dominance of surface-solution termination is also put forward, considering two extreme diffusion modes, i.e., translational and segmental. With the translational mode termination is largely suppressed and the living limit is mimicked, whereas with the segmental mode termination occurs more and the termination front moves upward alongside the polymer layer growth. In any case, bimodalities are established for the tethered chains both on the level of the chain length distribution and the MHD.

Modeling of Reversible Deactivation Radical Polymerization of Vinyl Monomers Promoted by Redox Initiation Using NHPI and Xanthone

AbstractTwo mathematical approaches for modeling of the kinetics and evolution of molar mass distributions in the reversible deactivation radical polymerization of vinyl monomers promoted by redox reaction with N‐hydroxyphthalimide (NHPI) and xanthone (XT) are presented. In the first modeling approach, the polymerization scheme is implemented in the standard version of the Predici commercial software. In the second case, an accelerated, self‐implemented version of the so called kinetic Monte Carlo (kMC) approach, considering binary trees, is used. The effect of concentrations of XT and monomer, as well as monomer type, on monomer conversion, NHPI efficiency, molar mass averages, molar mass dispersity, and full molar mass distributions are studied. The models are validated using literature available experimental data of polymerizations of methyl methacrylate (MMA) and styrene, in toluene, at 70 °C. The calculated results indicate that NHPI initiator efficiencies are low (<0.2); polymer end‐group functionalities present a maximum value of about 0.8 with a subsequent decrease with monomer conversion; molar mass distributions are broad, exhibiting low molar mass tails. In addition, the hypothetical copolymerization of styrene and MMA is also considered. Copolymer composition distributions for short molecules are broader than those for large ones.

Glycopolymer Brushes by Reversible Deactivation Radical Polymerization: Preparation, Applications, and Future Challenges.

The cellular surface contains specific proteins, also known as lectins, that are carbohydrates receptors involved in different biological events, such as cell–cell adhesion, cell recognition and cell differentiation. The synthesis of well-defined polymers containing carbohydrate units, known as glycopolymers, by reversible deactivation radical polymerization (RDRP) methods allows the development of tailor-made materials with high affinity for lectins because of their multivalent interaction. These polymers are promising candidates for the biomedical field, namely as novel diagnostic disease markers, biosensors, or carriers for tumor-targeted therapy. Although linear glycopolymers are extensively studied for lectin recognition, branched glycopolymeric structures, such as polymer brushes can establish stronger interactions with lectins. This specific glycopolymer topology can be synthesized in a bottlebrush form or grafted to/from surfaces by using RDRP methods, allowing a precise control over molecular weight, grafting density, and brush thickness. Here, the preparation and application of glycopolymer brushes is critically discussed and future research directions on this topic are suggested.

Merging New Organoborane Chemistry with Living Radical Polymerization

In this issue of Cell Reports Physical Science, Pan and co-workers synthesize alkylcatecholboranes that can be oxidized by oxygen to drive the release of carbon-centered radicals for initiating reversible addition-fragmentation chain transfer (RAFT) polymerization. These organoboranes can slowly decompose to radicals that enable RAFT polymerization with exceptional control yielding ultra-high molecular weight (UHMW) polymers.

Morpholine‐based RAFT agents for the reversible deactivation radical polymerization of vinyl acetate and N‐vinylimidazole

AbstractReversible addition–fragmentation chain transfer (RAFT) polymerization of less‐activated monomers in a controlled fashion is challenging due to the high reactivity and instability of the propagating radicals. We have designed dithiocarbamate‐based RAFT agents with morpholine as activating ‘Z’ group and benzyl, ethyl(1‐ethanoate)yl, ethyl(2‐propanoate)yl and cyanomethyl as ‘R’ leaving groups and investigated them for the reversible deactivation radical polymerization of vinyl acetate (VAc) and N‐vinylimidazole (N‐VIm). RAFT polymerization of VAc and N‐VIm at 70 °C using azobisisobutyronitrile as a free radical initiator proceeded in a controlled fashion as demonstrated by a linear increase in molar mass with conversion. Interestingly, the polymerization of VAc followed fast kinetics (approx. 60 min) with good to moderate control affording high‐molar‐mass poly(VAc) polymers. Furthermore, the synthesized chain transfer agents were able to polymerize N‐VIm under controlled conditions. The morpholine RAFT agents bearing cyanomethyl and ethyl(2‐propanoate)yl leaving groups showed better control of the polymerization of VAc and N‐VIm compared to the others. © 2020 Society of Chemical Industry

Aggregation-Induced Emission Active Polyacrylates via Cu-Mediated Reversible Deactivation Radical Polymerization with Bioimaging Applications.

The introduction of aggregation-induced emission (AIE) moieties into polymers results in smart materials with AIE characteristics, expanding their scope of applications. Herein, well-defined polymers with controlled molecular weight, low dispersity, and high end-group fidelity areproducedvia copper(0)-mediated reversible-deactivation radical polymerizations (Cu(0)-RDRPs). An AIE-containing initiator tetraphenylethene bromoisobutyrate (TPEBIB) has been synthesized, fully characterized, and utilized for the construction of different polyacrylate homopolymers and block copolymers bearing the TPE group with a range of molecular weights and architectures. All of the polymers exhibited AIE behavior. Notably, the hydrophobic TPE-poly(tert-butyl acrylate) (TPE-PtBA)-containing block copolymers are transformed to TPE-poly(acrylic acid) (TPE-PAA)-based amphiphilic copolymers by facile deprotection, enabling pH-tunable self-assembly in aqueous media to give fluorescent nanoparticles with various sizes. The low cytotoxicity, high specificity, and excellent photostability render them promising candidates as lysosome-specific probes in biological imaging applications.

Effect of ϒ- irradiation and study of ϒ-induced physico-chemical changes in high performance thermoset obtained by double cycloaddition of munchnone and bis-maleimide

ABSTRACT Techniques in polymer synthesis are taking different dimensions in the last few decades. Reversible-deactivation radical polymerization processes resulted in a wide range of polymeric architectures made from an almost infinite reservoir of functional building blocks. The concept of click chemistry revolutionized the way how polymer chemists approached synthetic routes. Among the few reactions that could qualify as click approach; the copper-catalyzed azide–alkyne cycloaddition reaction is in the front place. Whether click or not, cycloadditions are powerful tools for designing polymeric materials in a modular fashion, with a high level of functionality and, sometimes responsiveness. Thus we have developed an efficient synthetic platform for the preparation of a new class of polyimide-based high-performance thermosets (HPTs) based on the double 1,3-dipolar cycloaddition of munchnone with bis-maleimides. It is worth mentioning that this report is the first to deal with the changes in physico-chemical properties of HPTs obtained by cycloaddition reaction due to gamma irradiation. The polymers synthesized by this unique technique were irradiated with gamma doses in the range 10–300 kGy. The consequential effect of gamma radiation and the structural modifications induced on HPTs have been studied and discussed as a function of dose using different characterization techniques such as Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), Field Emission Scanning Electron Microscopy (FESEM) and UV-Vis Spectroscopy.

Bottlebrush Glycopolymers from 2-Oxazolines and Acrylamides for Targeting Dendritic Cell-Specific Intercellular Adhesion Molecule-3-Grabbing Nonintegrin and Mannose-Binding Lectin.

Lectins are omnipresent carbohydrate binding proteins that are involved in a multitude of biological processes. Unearthing their binding properties is a powerful tool toward the understanding and modification of their functions in biological applications. Herein, we present the synthesis of glycopolymers with a brush architecture via a "grafting from" methodology. The use of a versatile 2-oxazoline inimer was demonstrated to open avenues for a wide range of 2-oxazoline/acrylamide bottle brush polymers utilizing aqueous Cu-mediated reversible deactivation radical polymerization (Cu-RDRP). The polymers in the obtained library were assessed for their thermal properties in aqueous solution and their binding toward the C-type animal lectins dendritic cell-specific intercellular adhesion molecule-3-grabbing nonintegrin (DC-SIGN) and mannose-binding lectin (MBL) via surface plasmon resonance spectrometry. The encapsulation properties of a hydrophobic drug-mimicking compound demonstrated the potential use of glyco brush copolymers in biological applications.

1,8-Naphthalimide-Based Polymers Exhibiting Deep-Red Thermally Activated Delayed Fluorescence and Their Application in Ratiometric Temperature Sensing.

A series of naphthalimide (NAI)-based red-emissive thermally activated delayed fluorescence (TADF) acrylic monomers has been designed and synthesized. When copolymerized with a host material by Cu(0)-reversible deactivation radical polymerization (Cu(0)-RDRP), polymers exhibiting orange to deep-red TADF were obtained with quantum yields of up to 58% in solution and 31% in the solid state. These emitters exhibit dual emission consisting of high-energy prompt fluorescence from the NAI acceptor (λmax = 340 nm in toluene) and red-delayed fluorescence from the charge-transfer process (λmax = 633-711 nm in toluene). This dual emissive property was utilized to create red-to-blue temperature-responsive polymers by copolymerization of NAI-DMAC with N-isopropylacrylamide and a blue fluorescent dopant. These polymers exhibit red TADF at room temperature and blue fluorescence at 70 °C, with a high ratiometric fluorescent thermal response of 32 ± 4% K-1. Such systems are anticipated to have utility in bioimaging, drug delivery, and temperature sensing, further expanding the range of applications for red TADF materials.

Brush Copolymers from 2-Oxazoline and Acrylic Monomers via an Inimer Approach

Brush-shaped macromolecular architectures provide unique material properties because of their dense branched structures. However, there are major challenges in obtaining brush-shaped macromolecules when the required functional monomers are not compatible for copolymerization using the same synthetic technique. Herein, we present an inimer molecule structure that has both an initiating group for Cu-mediated radical polymerization and a 2-oxazoline monomer ring for cationic ring-opening polymerization. Thus, various combinations of poly(2-oxazoline-brush-acrylate/acrylamide) copolymers could be obtained by grafting from a poly(2-oxazoline) backbone bearing radical initiator units. A simple two-step synthesis method for a novel 2-oxazoline inimer was established and used in the homo and block copolymerization with 2-ethyl-2-oxazoline to yield the brush initiator structure. Moreover, selected acrylates and acrylamides were utilized for Cu(0)-mediated reversible deactivation radical polymerization (RDRP) initiated through the brush initiator. Finally, because of the understanding obtained via optimization reactions, high/low density, block, and amphiphilic brush copolymers with narrow molecular weight distributions were successfully obtained.

A Methoxyamine-Protecting Group for Organic Radical Battery Materials-An Alternative Approach.

An alternative synthetic route towards the widely employed electroactive poly(TEMPO methacrylate) (PTMA) via a thermally robust methoxyamine-protecting group is demonstrated herein. Protection of the radical moiety of hydroxy-TEMPO with a methyl functionality and subsequent esterification with methacrylic anhydride allows the high-yielding formation of the novel monomer methyl-TEMPO methacrylate (MTMA). The polymerization of MTMA to poly(MTMA) (PMTMA) is investigated via free radical polymerization and reversible addition-fragmentation chain-transfer polymerization (RAFT), a reversible-deactivation radical polymerization technique. Cleavage of the temperature-stable methoxyamine functionality by oxidative treatment of PMTMA with meta-chloroperbenzoic acid (mCPBA) releases the electroactive PTMA. The redox activity of PTMA was confirmed by cyclic voltammetry in lithium-ion coin cells.

Hydroxypropyl β‐Cyclodextrin Solubilizing Hydrophobic Initiator to Initiate Copper‐Mediated RDRP of NIPAM in Aqueous Media

AbstractThe copper mediated reversible deactivation radical polymerization (Cu0‐RDRP) can realize the precise synthesis of vinyl polymers in aqueous media. To our best of knowledge, there are few hydrophobic initiators directly utilized to perform the aqueous Cu0‐RDRP because the heterogeneity usually causes the polymerization to go out of control. This article first describes a very small number of hydroxylpropyl β‐cyclodextrins (HP‐β‐CDs) enabling to solubilize a bifunctional hydrophobic initiator tetraethylene glycol bis(2‐bromoisobutyrate) (T2B) into water to initiate the homogeneous Cu0‐RDRP of N‐isopropylacrylamide (NIPAM) giving rise to well‐defined poly(N‐isopropylacrylamide) (PNIPAM). The solubilization action is arisen from the inclusion complexation of HP‐β‐CDs with T2B as evidenced by 2D NOESY and 2D DOSY NMR analyses. Furthermore these entrapped HP‐β‐CDs show little effect on the polymerization process as they all skip off the initiator at the very beginning of the polymerization as determined by GPC and 1H NMR measurements.

Well-Defined Linear and Grafted Poly(2-isopropenyl-2-oxazoline)s Prepared via Copper-Mediated Reversible-Deactivation Radical Polymerization Methods

2-Isopropenyl-2-oxazoline (IPOx) is an important double functional monomer with multiple potential applications. However, until now, the attempts at reversible-deactivation radical polymerization (...

Photoinduced Modulation of Polymeric Interfacial Behavior Controlling Thin-Film Block Copolymer Wetting.

The tunable surface-wetting properties of photosensitive random copolymer mats were used to spatially control the orientations of thin-film block copolymer (BCP) structures. A photosensitive mat was produced via thermal treatment on spin-coated random copolymers of poly(styrene-ran-2-nitrobenzyl methacrylate-ran-glycidyl methacrylate), synthesized via reversible-deactivation radical polymerization. The degree of UV-induced deprotection of the nitrobenzyl esters in the mat was precisely controlled through the amount of UV-irradiation energy imparted to the mat. The resulting polarity switching of the constituents collectively altered the interfacial wetting properties of the mat, and the tunability allowed lamellar or cylinder-forming poly(styrene-b-methyl methacrylate) BCP thin films, applied over the mat, to change the domain orientation from perpendicular to parallel at proper UV exposures. UV irradiation passing through a photomask was capable of generating defined regions of BCP domains with targeted orientations.

Thermal responsive poly(N-isopropylacrylamide) grafted chicken feather keratin prepared via surface initiated aqueous Cu(0)-mediated RDRP: Synthesis and properties

Poultry chicken feather keratin was extracted and then modified for the fabrication of keratin-graft-PNIPAM copolymers. The keratin was well extracted from feather fiber and powdered. Subsequently, it underwent the surficial functionalization process with initiator groups. After the study conducted full disproportionation of Cu(I)Br/Me6Tren into Cu(0) and Cu(II)Br2 in the solvent, surface initiated aqueous Cu(0)-mediated reversible-deactivation radical polymerization (RDRP) of N-isopropylacrylamide (NIPAM) was performed in a methanol/water mixture solvent. The reaction was performed rapidly and efficiently, during which over 100% graft rate was achieved at 60 min. After 6 h reaction, 200% graft rate could be achieved. High graft rate (up to 287%) was achieved, and graft rate could be regulated by controlling the reaction time and the addition of monomer. The fabricated keratin-g-PNIPAM exhibited a rough surface. As revealed from the results of thermal analysis, the thermal stability of keratin-g-PNIPAM was enhanced noticeably compared with the original keratin. Besides, grafted PNIPAM chains exhibited a higher glass transition temperature. The grafted keratin particles displayed enhanced hydrophilicity. Keratin-g-PNIPAMs exhibit a lower LCST comparing to homopolymer and the flocculation in hot water behavior could be controlled by regulating graft rate.