Showing papers on "Copolymer published in 2019"
TL;DR: Alternative PISA protocols are paid particular attention to, which allow the preparation of nanoparticles with improved control over copolymer morphology and functionality, and have been optimized via high-throughput polymerization and recently evaluated within flow reactors for facile scale-up syntheses.
Abstract: In this Perspective, we summarize recent progress in polymerization-induced self-assembly (PISA) for the rational synthesis of block copolymer nanoparticles with various morphologies. Much of the PISA literature has been based on thermally initiated reversible addition–fragmentation chain transfer (RAFT) polymerization. Herein, we pay particular attention to alternative PISA protocols, which allow the preparation of nanoparticles with improved control over copolymer morphology and functionality. For example, initiation based on visible light, redox chemistry, or enzymes enables the incorporation of sensitive monomers and fragile biomolecules into block copolymer nanoparticles. Furthermore, PISA syntheses and postfunctionalization of the resulting nanoparticles (e.g., cross-linking) can be conducted sequentially without intermediate purification by using various external stimuli. Finally, PISA formulations have been optimized via high-throughput polymerization and recently evaluated within flow reactors for facile scale-up syntheses.
339 citations
TL;DR: This Minireview summarizes some of the recent progress in the extensively studied Brookhart and Drent catalyst systems, as well as emerging alternative palladium and nickel catalysts.
Abstract: Transition-metal-catalyzed copolymerization of olefins with polar monomers represents a challenge because of the large variety of substrate-induced side reactions. However, this approach also holds the potential for the direct synthesis of polar functionalized polyolefins with unique properties. After decades of research, only a few catalyst systems have been found to be suitable for this reaction. Some major advances in catalyst development have been made in the past five years. This Minireview summarizes some of the recent progress in the extensively studied Brookhart and Drent catalyst systems, as well as emerging alternative palladium and nickel catalysts.
242 citations
TL;DR: This review highlights the challenges associated with conventional polymerization systems and evaluates the most relevant methods which have been developed to 'bridge the gap' between polar vinyl monomers and α-olefins.
Abstract: The inherent differences in reactivity between activated and non-activated alkenes prevents copolymerization using established polymer synthesis techniques. Research over the past 20 years has greatly advanced the copolymerization of polar vinyl monomers and olefins. This Review highlights the challenges associated with conventional polymerization systems and evaluates the most relevant methods which have been developed to "bridge the gap" between polar vinyl monomers and olefins. We discuss advancements in heteroatom tolerant coordination-insertion polymerizations, methods of controlling radical polymerizations to incorporate olefinic monomers, as well as combined approaches employing sequential polymerizations. Finally, we discuss state-of-the-art stimuli-responsive systems capable of facile switching between catalytic pathways and provide an outlook towards applications in which tailored copolymers are ideally suited.
136 citations
TL;DR: This scalable PISA approach offers facile access to ordered inverse mesophases, significantly expanding the PISA morphology scope and enabling its applicability to the materials science fields.
Abstract: Block copolymer particles with controlled morphologies are of great significance in nanomaterials and nanotechnology. However, ordered inverse morphologies are difficult to achieve due to complex mechanism and formation conditions. Here we report scalable preparation of amphiphilic alternating block copolymer particles with inverse bicontinuous mesophases via polymerization-induced self-assembly (PISA). Concentrated dispersion copolymerizations (up to 40% solid content) of styrene (St) and pentafluorostyrene (PFS) employing a short poly(N,N-dimethylacrylamide) (PDMA29) stabilizer block lead to the formation of well-defined, highly asymmetric PDMA29-b-P(St-alt-PFS)x block copolymers with precise compositions and various morphologies, from simple spheres to ordered inverse cubosome mesophases. The particle morphology is affected by the molecular weight, solid content, and nature of the cosolvents. The cubosome structure is confirmed by electron microscopies and small angle X-ray scattering spectroscopy. This scalable PISA approach offers facile access to ordered inverse mesophases, significantly expanding the PISA morphology scope and enabling its applicability to the materials science fields.
119 citations
TL;DR: In this article, a simple, scalable, bench-top approach to covalently tethered nylon-MOF polymer composite materials through an interfacial polymerization technique was presented, which demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl-4-nitrophenyl phosphate, DMNP) compared to MOFs that are non-covalently, physically entrapped in nylon, thus highlighting the importance of MOF-polymer hybridization.
Abstract: Hybridization of metal-organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF-polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench-top approach to covalently tethered nylon-MOF polymer composite materials through an interfacial polymerization technique. The copolymerization of a modified UiO-66-NH2 MOF with a growing polyamide fiber (PA-66) during an interfacial polymerization gave hybrid materials with up to around 29 weight percent MOF. The covalent hybrid material demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl-4-nitrophenyl phosphate, DMNP) compared to MOFs that are non-covalently, physically entrapped in nylon, thus highlighting the importance of MOF-polymer hybridization.
117 citations
TL;DR: A new class of self-healing materials is formed by the copolymerization of ethylene and anisyl-substituted propylenes using a sterically demanding half-sandwich scandium catalyst, affording unique multi-block copolymers composed of relatively long alternating ethylene- alt-anisylpropylene sequences and short Ethylene-ethylene units.
Abstract: Self-healing materials are of fundamental interest and practical importance. Herein we report the synthesis of a new class of self-healing materials, formed by the copolymerization of ethylene and anisyl-substituted propylenes using a sterically demanding half-sandwich scandium catalyst. The copolymerization proceeded in a controlled fashion, affording unique multi-block copolymers composed of relatively long alternating ethylene-alt-anisylpropylene sequences and short ethylene–ethylene units. By controlling the molecular weight and varying the anisyl substituents, a series of copolymers that show a wide range of glass-transition temperatures (Tg) and mechanical properties have been obtained. The copolymers with Tg below room temperature showed high elastic modulus, high toughness, and remarkable self-healability, being able to autonomously self-heal upon mechanical damage not only in a dry environment but also in water and aqueous acid and alkaline solutions, while those with Tg around or above room temp...
111 citations
TL;DR: In this article, a series of tetrablock copolymers containing an all-hydrocarbon backbone were synthesized, and they were cast into membranes with an ion-exchange capacity between 1.55 and 2.60 milliequivalents per gram (meq/g).
104 citations
TL;DR: In this paper, surface-initiated photoinduced electron transfer-reversible addition-fragmentation chain transfer polymerization (SI-PET-RAFT) is introduced, which affords functionalization of surfaces with spatiotemporal control and provides oxygen tolerance under ambient conditions.
Abstract: In this communication, surface-initiated photoinduced electron transfer-reversible addition–fragmentation chain transfer polymerization (SI-PET-RAFT) is introduced. SI-PET-RAFT affords functionalization of surfaces with spatiotemporal control and provides oxygen tolerance under ambient conditions. All hallmarks of controlled radical polymerization (CRP) are met, affording well-defined polymerization kinetics, and chain end retention to allow subsequent extension of active chain ends to form block copolymers. The modularity and versatility of SI-PET-RAFT is highlighted through significant flexibility with respect to the choice of monomer, light source and wavelength, and photoredox catalyst. The ability to obtain complex patterns in the presence of air is a significant contribution to help pave the way for CRP-based surface functionalization into commercial application.
101 citations
TL;DR: This work synthesized AAEMs consisting of polyethylene backbones and alkaline-stable imidazolium cations via the living ring-opening metathesis polymerization of trans-cyclooctene monomers, wherein either block or random copolymer sequences can be achieved.
Abstract: Alkaline anion exchange membranes (AAEMs) are an important component of alkaline exchange membrane fuel cells (AEMFCs), which facilitate the efficient conversion of fuels to electricity using nonplatinum electrode catalysts. However, low hydroxide conductivity and poor long-term alkaline stability of AAEMs are the major limitations for the widespread application of AEMFCs. In this paper, we report the synthesis of highly conductive and chemically stable AAEMs from the living polymerization of trans-cyclooctenes. A trans-cyclooctene–fused imidazolium monomer was designed and synthesized on gram scale. Using these highly ring-strained monomers, we produced a range of block and random copolymers. Surprisingly, AAEMs made from the random copolymer exhibited much higher conductivities than their block copolymer analogs. Investigation by transmission electron microscopy showed that the block copolymers had a disordered microphase segregation which likely impeded ion conduction. A cross-linked random copolymer demonstrated a high level of hydroxide conductivity (134 mS/cm at 80 °C). More importantly, the membranes exhibited excellent chemical stability due to the incorporation of highly alkaline-stable multisubstituted imidazolium cations. No chemical degradation was detected by 1H NMR spectroscopy when the polymers were treated with 2 M KOH in CD3OH at 80 °C for 30 d.
99 citations
TL;DR: A class of readily available bifunctional silyl ether-based cyclic olefins that copolymerize efficiently with norbornene-based (macro)monomers to provide copolymers with backbone degradability under mildly acidic aqueous conditions and degradation rates that can be tuned over several orders of magnitude, depending on the sily l ether substituents.
Abstract: Ring-opening metathesis polymerization of norbornene-based (macro)monomers is a powerful approach for the synthesis of macromolecules with diverse compositions and complex architectures. Nevertheless, a fundamental limitation of polymers prepared by this strategy is their lack of facile degradability, limiting their utility in a range of applications. Here we describe a class of readily available bifunctional silyl ether-based cyclic olefins that copolymerize efficiently with norbornene-based (macro)monomers to provide copolymers with backbone degradability under mildly acidic aqueous conditions and degradation rates that can be tuned over several orders of magnitude, depending on the silyl ether substituents. These monomers can be used to manipulate the in vivo biodistribution and clearance rate of polyethylene glycol-based bottlebrush polymers, as well as to synthesize linear, bottlebrush and brush-arm star copolymers with degradable segments. We expect that this work will enable preparation of degradable polymers by ROMP for biomedical applications, responsive self-assembly and improved sustainability.
93 citations
TL;DR: Bromoalkyl functionalized poly(olefin)s were synthesized by copolymerization of 4-(4-methylphenyl)-1-butene with 11-bromo-1-undecene using Ziegler-Natta polymerization.
Abstract: Bromoalkyl-functionalized poly(olefin)s were synthesized by copolymerization of 4-(4-methylphenyl)-1-butene with 11-bromo-1-undecene using Ziegler–Natta polymerization. The resulting bromoalkyl-fun...
TL;DR: In this article, a new generation of α-diimine Ni(II) and Pd-II catalysts for tuning the catalytic activity, polymer molecular weight, comonomer incorporation, and branching density in ethylene polymerization and copolymerization with polar monomers were presented.
TL;DR: It is shown here that copolymerization of kinetically trapped states of one PBI with seeds of another PBI leads to the formation of supramolecular block copolymers by chain-growth process from the seed termini as confirmed by UV/vis spectroscopy and atomic force microscopy.
Abstract: Living covalent polymerization has been a subject of intense research for many decades and has culminated in the synthesis of a large variety of block copolymers (BCPs) with structural and function...
TL;DR: A new approach to radical ring-opening polymerization is presented that employs a new thionolactone monomer to generate polymers with thioester-containing backbones that readily degrade under hydrolytic conditions and permits the synthesis of block polymers for the preparation of well-defined macromolecular structures.
Abstract: A new approach to radical ring-opening polymerization is presented that employs a new thionolactone monomer to generate polymers with thioester-containing backbones. The use of a thiocarbonyl acceptor overcomes longstanding reactivity problems in the field to give complete ring-opening and quantitative incorporation into a variety of acrylate polymers. The resulting copolymers readily degrade under hydrolytic conditions, in addition to cysteine-mediated degradation through transthioesterification. The strategy is compatible with reversible addition–fragmentation chain transfer (RAFT) polymerization and permits the synthesis of block polymers for the preparation of well-defined macromolecular structures.
TL;DR: The results prove that the introduction of the templating bis-urea stickers into PISA greatly promotes the formation of fibres in a large experimental window.
Abstract: Dispersions of block copolymer fibres in water have many potential applications and can be obtained by polymerization-induced self-assembly (PISA), but only under very restricted experimental conditions. In order to enlarge this experimental window, we introduced a supramolecular moiety, a hydrogen-bonded bis-urea sticker, in the macromolecular reversible addition fragmentation chain transfer (RAFT) agent to drive the morphology of the nano-objects produced by RAFT-mediated PISA towards the fibre morphology. This novel concept is tested in the synthesis of a series of poly(N,N-dimethylacrylamide)-b-poly(2-methoxyethyl acrylate) (PDMAc-b-PMEA) diblock copolymers prepared by dispersion polymerization in water. The results prove that the introduction of the templating bis-urea stickers into PISA greatly promotes the formation of fibres in a large experimental window.
TL;DR: This newly-synthesized, tunable, cellulose-based double barrier system exhibits a pH-triggered, prolonged, and slow-release profile based on the release test using both Nile Red dye and doxorubicin.
TL;DR: Derry et al. as mentioned in this paper proposed a phase diagram for the formation of sterically-stabilized poly(glycerol monomethacrylate) (PGMA)-PMOEMA spheres, worms or vesicles.
Abstract: Polymerization-induced self-assembly (PISA) is a powerful platform technology for the rational and efficient synthesis of a wide range of block copolymer nano-objects (e.g., spheres, worms or vesicles) in various media. In situ small-angle X-ray scattering (SAXS) studies of reversible addition–fragmentation chain transfer (RAFT) dispersion polymerization have previously provided detailed structural information during self-assembly (see M. J. Derry et al., Chem. Sci. 2016, 7, 5078–5090). However, conducting the analogous in situ SAXS studies during RAFT aqueous emulsion polymerizations poses a formidable technical challenge because the inherently heterogeneous nature of such PISA formulations requires efficient stirring to generate sufficiently small monomer droplets. In the present study, the RAFT aqueous emulsion polymerization of 2-methoxyethyl methacrylate (MOEMA) has been explored for the first time. Chain extension of a relatively short non-ionic poly(glycerol monomethacrylate) (PGMA) precursor block leads to the formation of sterically-stabilized PGMA-PMOEMA spheres, worms or vesicles, depending on the precise reaction conditions. Construction of a suitable phase diagram enables each of these three morphologies to be reproducibly targeted at copolymer concentrations ranging from 10 to 30% w/w solids. High MOEMA conversions are achieved within 2 h at 70 °C, which makes this new PISA formulation well-suited for in situ SAXS studies using a new reaction cell. This bespoke cell enables efficient stirring and hence allows in situ monitoring during RAFT emulsion polymerization for the first time. For example, the onset of micellization and subsequent evolution in particle size can be studied when preparing PGMA29-PMOEMA30 spheres at 10% w/w solids. When targeting PGMA29-PMOEMA70 vesicles under the same conditions, both the micellar nucleation event and the subsequent evolution in the diblock copolymer morphology from spheres to worms to vesicles are observed. These new insights significantly enhance our understanding of the PISA mechanism during RAFT aqueous emulsion polymerization.
TL;DR: In this paper, the authors provide background information about the development of lignin-based copolymer adhesives for the production of composite wood panels as well as the future prospects of these adhesive in industry.
TL;DR: In this paper, photo-initiated polymerization-induced self-assembly (photo-PISA) based on aqueous visible light-induced reversible addition-fragmentation chain transfer (RAFT)-mediated emulsion polymerization at room temperature is presented.
Abstract: Aqueous emulsion polymerization is one of the most commonly used techniques in industry for the production of polymer latexes. In this contribution, we present photoinitiated polymerization-induced self-assembly (photo-PISA) based on aqueous visible light-induced reversible addition–fragmentation chain transfer (RAFT)-mediated emulsion polymerization at room temperature. A wide range of morphologies including spheres, worms, and vesicles have been achieved at room temperature by modulating reaction parameters. Additionally, this method enables access to inorganic nanoparticles-loaded vesicles by adding inorganic nanoparticles at the beginning of the polymerization. Finally, an oxygen-tolerant RAFT-mediated emulsion polymerization has been developed, allowing the synthesis of polymer nano-objects at low volumes (e.g., in a 96-well plate). This study is expected to expand the scope of photo-PISA for the preparation of various block copolymer nano-objects in water at room temperature.
TL;DR: Self‐consistent mean field theory suggests this rich self‐assembly behavior is the result of the greater degree of hydration of the PHPMA block at lower temperature, which is in agreement with variable temperature 1H NMR studies.
Abstract: It is well‐known that the self‐assembly of AB diblock copolymers in solution can produce various morphologies depending on the relative volume fraction of each block. Recently, polymerization‐induced self‐assembly (PISA) has become widely recognized as a powerful platform technology for the rational design and efficient synthesis of a wide range of block copolymer nano‐objects. In this study, PISA is used to prepare a new thermoresponsive poly(N‐(2‐hydroxypropyl) methacrylamide)‐poly(2‐hydroxypropyl methacrylate) [PHPMAC‐PHPMA] diblock copolymer. Remarkably, TEM and SAXS studies indicate that a single copolymer composition can form well‐defined spheres (4 °C), worms (22 °C) or vesicles (50 °C) in aqueous solution. Given that the two monomer repeat units have almost identical chemical structures, this system is particularly well‐suited to theoretical analysis. Self‐consistent mean field theory suggests this rich self‐assembly behavior is the result of the greater degree of hydration of the PHPMA block at lower temperature, which is in agreement with variable temperature 1H NMR studies.
TL;DR: A simple catalytic approach based on metal-free Lewis pair that breaks the limit of irreversible monomer enchainment order and yields ether-ester type block copolymers with unlimited sequences as well as widely variable compositions and architectures is reported.
Abstract: Polymerizing epoxides after cyclic esters remains a major challenge, though their block copolymers have been extensively studied and used for decades. Reported here is a simple catalytic approach based on a metal-free Lewis pair that addresses the challenge. When the Lewis acid is used in excess of a base, selective (transesterification-free) polymerization of epoxides occurs in the presence of esters, while selectivity toward cyclic esters is achieved by an oppositely biased catalyst. Hence, one-pot block copolymerization can be performed in both ester-first and ether-first orders with selectivity being switchable at any stage, yielding ether-ester-type block copolymers with unlimited ordering of sequences as well as widely variable compositions and architectures. The selectivity can also be switched back and forth several times to generate a multiblock copolymer. Experimental and calculational results indicate that the selectivity originates mainly from the state of catalyst-activated hydroxy species.
TL;DR: Four new terpolymers prepared from sulfur and two distinct alkene monomers that can be predictively tuned in glass transition, molecular weight, solubility, mechanical properties, and colour are reported.
Abstract: Sulfur is an underused by-product of the petrochemicals industry. Recent research into inverse vulcanization has shown how this excess sulfur can be transformed into functional polymers, by stabilization with organic crosslinkers. For these interesting new materials to realize their potential for applications, more understanding and control of their physical properties is needed. Here we report four new terpolymers prepared from sulfur and two distinct alkene monomers that can be predictively tuned in glass transition, molecular weight, solubility, mechanical properties, and color.
TL;DR: Wang et al. as mentioned in this paper proposed an integrated composites laboratory at the University of Tennessee, Knoxville, Tennessee, USA for the purpose of improving the performance of a composite material.
Abstract: J. Yang, W. Yang, Prof. X. Wang College of Materials Science and Engineering Chongqing University of Technology Chongqing 400054, China E-mail: wangxuanlun@cqut.edu.cn Prof. X. Wang State Key Laboratory of Polymer Materials Engineering Sichuan University Chengdu 610065, China M. Dong, Dr. H. Liu, Prof. Z. Guo Integrated Composites Laboratory Department of Chemical & Biomolecular, Engineering University of Tennessee Knoxville, TN 37996, USA E-mail: dmy1989melo@126.com; zguo10@utk.edu M. Dong, Dr. H. Liu Key Laboratory of Materials Processing and Mold (Zhengzhou University) Ministry of Education National Engineering Research Center for Advanced Polymer Processing Technology Zhengzhou University Zhengzhou 450002, China
TL;DR: The PSBMA-NaSS hydrogels collapsed when the ionic strength increased because the ions can weaken the repulsive interaction of the anionic groups of PNaSS, and showed high adsorption of methylene blue.
Abstract: In this work, we studied the swelling behavior and adsorption behavior of zwitterionic copolymer hydrogels, which were prepared via the free radical copolymerization of sulfobetaine methacrylate (SBMA) and other monomers including sodium p-styrenesulfonate (NaSS), acrylic acid, N-isopropylacrylamide, and 2-(dimethylamino) ethyl methacrylate. The PSBMA hydrogel showed increased swelling ratio with the increase of ionic strength at the same temperature, and the swelling process reflected endothermicity. Interestingly, the PSBMA-NaSS hydrogels collapsed when the ionic strength increased because the ions can weaken the repulsive interaction of the anionic groups of PNaSS. In addition, the PSBMA-NaSS showed high adsorption of methylene blue (760 mg/g). The zwitterionic hydrogels have potential to be used as an adsorbent in the field of wastewater treatment.
TL;DR: There was a significant decrease in the molecular weight if the aliphatic monomers were changed from diols to diacid ethyl esters, which provides a closer insight into the application of enzymatic polymerization techniques in designing sustainable high‐performance polymers.
Abstract: Enzymatic polymerization provides an excellent opportunity for the conversion of renewable resources into polymeric materials in an effective and sustainable manner. A series of furan-based copolyesters was synthesized with M w ‾ up to 35 kg mol-1 , by using Novozyme 435 as a biocatalyst and dimethyl 2,5-furandicarboxylate (DMFDCA), 2,5-bis(hydroxymethyl)furan (BHMF), aliphatic linear diols, and diacid ethyl esters as monomers. The synthetic mechanism was evaluated by the variation of aliphatic linear monomers and their feed compositions. Interestingly, there was a significant decrease in the molecular weight if the aliphatic monomers were changed from diols to diacid ethyl esters. The obtained copolyesters were thoroughly characterized and compared with their polyester analogs. These findings provide a closer insight into the application of enzymatic polymerization techniques in designing sustainable high-performance polymers.
TL;DR: The zwitterion-modified membrane is promising as a highly permeable fouling resistant cross-linked polyamide network for various water treatment applications.
Abstract: A simple scalable strategy is proposed to fabricate highly permeable antifouling nanofiltration membranes. Membranes with a selective thin polyamide layer were prepared via interfacial polymerization incorporating building blocks of zwitterionic copolymers. The zwitterionic copolymer, poly(aminopropyldimethylaminoethyl methacrylate)-co-poly(sulfobetaine methacrylate) with an average molecular weight of 6.1 kg mol–1, was synthesized in three steps: (i) polymerization of dimethylaminoethyl methacrylate to yield the base polymer by atom transfer radical polymerization (ATRP), (ii) fractional sulfobetainization via quaternization, and (iii) amination via quaternization. The effect of the zwitterionic polymer content on the polyamide surface characteristics, fouling resistance, and permeance is demonstrated. The zwitterion-modified membrane becomes more hydrophilic with lower surface roughness, as the zwitterionic polymer fraction increases. The excellent fouling resistance of the zwitterion-modified membrane ...
TL;DR: A general and robust strategy toward water-stable J-aggregated dye-templated nanoassemblies by incorporating an amphiphilic diblock copolymer and a stimuli-responsive dye as the only two building components is presented.
Abstract: Controlling the packing arrangements of dyes is a facile way of tuning their photophysical and/or photochemical properties, thus enabling new sensing mechanisms for photofunctional tools. Here, we present a general and robust strategy toward water-stable J-aggregated dye-templated nanoassemblies by incorporating an amphiphilic diblock copolymer and a stimuli-responsive dye as the only two building components. An iodo-substituted boron dipyrromethene (BODIPY) was adopted as a template to direct the self-assembly of poly(ethylene glycol)- block-polycaprolactone (PEG-PCL), forming a core-shell nanoplate with slip-stacked BODIPYs as core surrounded by hydrophilic PEG shell. The self-assembled nanoplate is stable in cell culture medium and possesses a built-in stimuli-responsiveness that arises from BODIPY bearing meso-carboxylate protecting group, which is efficiently removed upon treatment with peroxynitrite. The resulting negative charges lead to rearrangement of dyes from J-stacking to nonstacking, which activates photoinduced singlet oxygen production from the nanoassemblies. The stimuli-activatable photosensitivity has been exploited for specific photodynamic ablation of activated RAW 264.7 cells with excessive endogenous peroxynitrite. In light of the generality of the sensing mechanism, the concept described herein will significantly expand the palette of design principles to develop diverse photofunctional tools for biological research and clinical needs.
TL;DR: In this paper, a zwitterionic polymer with a sticky catechol chain end was successfully synthesized by ARGET-ATRP and used to modify membranes for separation of oil/water mixtures and emulsions.
TL;DR: A universal method to grow polymers on MOF surfaces with well-defined thickness, sequence and functionality.
Abstract: We report a generalizable approach to construct MOF@polymer functional composites through surface-initiated atom transfer radical polymerization (SI-ATRP). Unlike conventional SI-ATRP that requires covalent pre-anchoring of the initiating group on substrate surfaces, in our approach, a rationally designed random copolymer (RCP) macroinitiator first self-assembles on MOF surfaces through inter-chain hydrogen bond crosslinking. Subsequent polymerization in the presence of a crosslinking monomer covalently threads these polymer chains into a robust network, physically confining the MOF particle inside the polymer shell. We demonstrated the universality of this approach by growing various polymers on five MOFs of different metals (Zr, Zn, Co, Al, and Cr) with complete control over shell thickness, functionality and layer sequence while still retaining the inherent porosity of the MOFs. Moreover, the wettability of UiO-66 can be continuously tuned from superhydrophilic to superhydrophobic simply through judicious monomer(s) selection. We also demonstrated that a 7 nm polystyrene shell can effectively shield UiO-66 particles against 1 M H2SO4 and 1 M NaOH at elevated temperature, enabling their potential application in demanding chemical environments.
TL;DR: In this paper, a comparison of the mechanistic aspects of living and immortal polymerization processes is made, with the main difference between these two pathways being rapid and reversible chain transfer reactions involving protic impurities or additives.