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The copolymerization of carbon dioxide (CO2) and epoxides to produce aliphatic polycarbonates is a burgeoning technology for the large-scale utilization of CO2 and degradable polymeric materials. Even with the wealth of advancements achieved over the past 50 years on this green technology, many challenges remain, including the use of metal-containing catalysts for polymerization, the removal of the chromatic metal residue after polymerization, and the limited practicable epoxides, especially for those containing electron-withdrawing groups. Herein, we provide kinds of pinwheel-shaped tetranuclear organoboron catalysts for epichlorohydrin/CO2 copolymerization with >99% polymer selectivity and quantitative CO2 uptake (>99% carbonate linkages) under mild conditions (25-40 °C, 25 bar of CO2). The produced poly(chloropropylene carbonate) has the highest molecular weight of 36.5 kg/mol and glass transition temperature of 45.4 °C reported to date. The energy difference (ΔEa = 60.7 kJ/mol) between the cyclic carbonate and polycarbonate sheds light on the robust performance of our metal-free catalyst. Control experiments and density functional theory (DFT) calculations revealed a cyclically sequential copolymerization mechanism. The metal-free feature, high catalytic performance under mild conditions, and no trouble with chromaticity for the produced polymers imply that our catalysts are practical candidates to advance the CO2-based polycarbonates.

A series of highly active organoboron catalysts for the coupling of CO2 and epoxides with the advantages of scalable preparation, thermostability, and recyclability is reported. The metal-free catalysts show high reactivity towards a wide scope of cyclic carbonates (14 examples) and can withstand a high temperature up to 150 °C. Compared with the current metal-free catalytic systems that use mol % catalyst loading, the catalytic capacity of the catalyst described herein can be enhanced by three orders of magnitude (epoxide/cat.=200 000/1, mole ratio) in the presence of a cocatalyst. This feature greatly narrows the gap between metal-free catalysts and state-of-the-art metallic systems. An intramolecular cooperative mechanism is proposed and certified on the basis of investigations on crystal structures, structure-performance relationships, kinetic studies, and key reaction intermediates.

This manuscript describes a kind of bifunctional organocatalyst with unprecedented reactivity for the synthesis of polyethers via ring-opening polymerization (ROP) of epoxides under mild conditions. The bifunctional catalyst incorporates two 9-borabicyclo[3.3.1]nonane centers on the two ends as Lewis acidic sites for epoxide activation and a quaternary ammonium halide in the middle as the initiating site. The catalyst could be easily prepared in two steps from commercially available stocks on up to kilogram scale with ≈100 % yield. The organoboron catalyst mediated ROP of epoxides displays living behavior with low catalyst loading (5 ppm) and enables the synthesis of polyethers with molecular weights of over a million grams per mole (>106  g mol-1 ). Based on the investigations on crystal structure of catalyst, MALDI-TOF, and 11 B NMR spectroscopy, an intramolecular ammonium cation assisted SN 2 mechanism is proposed and verified by DFT calculations.

The metallic catalyst-dominated alternating copolymerization of CO2 and epoxides has flourished for 50 years; however, the involved multistep preparation of the catalysts and the necessity to remov...

The impact of thermal history on the kinetic response of thin thermoresponsive diblock copolymer poly(diethylene glycol monomethyl ether methacrylate)-block-poly(poly(ethylene glycol) methyl ether methacrylate), abbreviated as PMEO2MA-b-POEGMA300, films is investigated by in situ neutron reflectivity. The PMEO2MA and POEGMA300 blocks are both thermoresponsive polymers with a lower critical solution temperature. Their transition temperatures (TTs) are around 25 °C (TT1, PMEO2MA) and 60 °C (TT2, POEGMA300). Thus, by applying different temperature protocols (20 to 60 or 20 to 40 to 60 °C), the PMEO2MA-b-POEGMA300 thin films experience different thermal histories: the first protocol directly switches from a swollen to a collapsed state, whereas the second one switches first from a swollen to a semicollapsed and finally to a collapsed state. Although the applied thermal histories differ, the response and final state of the collapsed films are very close to each other. After the thermal stimulus, both films present a complicated response composed of an initial shrinkage, followed by a rearrangement. Interestingly, a subsequent reswelling of the collapsed film is only observed in the case of having applied a thermal stimulus of 20 to 40 °C. The normalized film thickness and the D2O amount of each layer in the PMEO2MA-b-POEGMA300 films are consistent at the end of the two different thermal stimuli. Hence, it can be concluded that the thermal history does not influence the final state of the PMEO2MA-b-POEGMA300 films upon heating. Based on this property, these thin films are especially suitable for the temperature switches on the nanoscale, which may experience different thermal histories.

The linear shrinkage behavior in thermoresponsive diblock copolymer films and its potential application in temperature sensors are investigated. The copolymer is composed of two thermoresponsive blocks with different transition temperatures (TTs): di(ethylene glycol) methyl ether methacrylate (MEO2MA; TT1 = 25 °C) and poly(ethylene glycol) methyl ether methacrylate (OEGMA300; TT2 = 60 °C) with a molar ratio of 1:1. Aqueous solutions of PMEO2MA-b-POEGMA300 show a three-stage transition upon heating as seen with optical transmittance and small-angle X-ray scattering: dissolution (T TT2). Due to the restrictions in the polymer chain arrangement introduced by the solid Si substrate, spin-coated PMEO2MA-b-POEGMA300 films exhibit an entirely different internal structure and transition behavior. Neutron reflectivity shows the absence of an ordered structure normal to the Si substrate in as-prepared PMEO2MA-b-POEGMA300 films. After exposure to D2O vapor for 3 h and then increasing the temperature above its TT1 and TT2, the ordered structure is still not observed. Only a D2O enrichment layer is formed close to the hydrophilic Si substrate. Such PMEO2MA-b-POEGMA300 films show a linear shrinkage between TT1 and TT2 in a D2O vapor atmosphere. This special behavior can be attributed to the synergistic effect between the restrained collapse of the PMEO2MA blocks by the still swollen POEGMA300 blocks and the impedance of chain arrangement by the Si substrate. Based on this unique behavior, spin-coated PMEO2MA-b-POEGMA300 films are further prepared into a temperature sensor by implementing Ag electrodes. Its resistance decreases linearly with temperature between TT1 and TT2.

The performances of lithium-ion batteries (LIBs) are dependent on the wettability and stability of porous separators. Musselinspired coatings seem to be useful to improve the surface wettability of commercialized polyolefin separators. However, it is still a challenge to guarantee their stability under polar electrolytes. Herein, we report a facile and versatile way to enhance the wettability and stability of polypropylene separators by constructing robust polydopamine (PDA) coatings triggered with CuSO4/H2O2. These coatings were conveniently deposited on the polypropylene separator surfaces and the PDA-coated separators exhibited the improved surface wettability and thermal stability. The electrolyte uptake increased nearly two folds from the pristine separator to the modified ones. Correspondingly, the ionic conductivity also rose from 0.82 mS·cm-1 to 1.30 mS·cm-1. Most importantly, the CuSO4/H2O2-triggered PDA coatings were very stable under strong polar electrolytes, endowing the cells with excellent cycle performance and enhanced C-rate capacity. Overall, the results unequivocally demonstrate that application of PDA coatings on polyolefin separator triggered by CuSO4/H2O2 is a facile and efficient method for improving the wettability and stability of separators for high LIBs performance.

The first example of CO2-based thermoset elastomers (CO2Es) on the basis of two sustainable and degradable polymers, rigid CO2-based polycarbonates and soft polyesters, is reported. The elastomers exhibit acceptable mechanical strength and excellent elasticity (average elastic recovery >93%) by introducing a chemical network. By adjusting the ratio of rigid CO2 polycarbonate/soft polyester, green elastomers with adjustable mechanical performance are obtained efficiently.

The copolymerization of carbon dioxide (CO2) with epoxides via organocatalysis is still a big challenge. This work reports the selective copolymerization of CO2 and epoxides bearing a phenyl group, i.e., phenyl glycidyl ether (PGE) and styrene oxide (StO), catalyzed by a combination of Lewis bases (LBs) and excess triethyl borane (TEB). The resultant CO2/PGE copolymers presented a molar fraction of carbonate units (FCO2) of more than 99%, with a regioregularity of ca. 92%. The weight percentage of the cyclic carbonate (WCC) was less than 1 wt%. The turnover frequency (TOF) was as high as 38 h−1 for producing the CO2/PGE copolymer with a number-average molecular weight (Mn) of 16.6 kg mol−1 and a dispersity (Đ) of 1.2. What is of importance is that the dosage of TEB had a strong impact on the selectivity, where the regioregular copolymer or cyclic carbonate could be selectively produced by simply tuning the TEB/LB molar ratios, as revealed by in situ FT-IR spectroscopy. It is proposed that excess TEB could either promote the equilibrium to generate the TEB-coordinated growing anion or activate the epoxide for enhancing the reactivity. Both copolymers are promising optical materials as colorless solids with a high refractive index (nd) of 1.55–1.56 (590 nm, 20 °C, cast film).

The alternating copolymerization of CO2/epoxides to polycarbonates (CO2–PCs) has been an area of research focus because of the growing concern about energy and the environment. Regardless of the enormous progress that has been made, the lack of functionalities and inert chemical structure of CO2-based polycarbonates greatly limit the scope of the application in practice. With an aim to develop smart materials with high added-value, herein, the CO2-based thermoplastic elastomers (CO2-TPEs) were first reported. The CO2-TPEs are efficiently constructed in a tandem catalysis process, which includes epoxide hydrolysis reaction, immortal alternating polymerization of carbon dioxide and epoxides, and the thiol–ene click chemistry. The CO2-TPEs exhibit characteristic properties of thermoplastic elastomers with a Young’s modulus up to 10.1 MPa. Moreover, robust self-healing ability could be endowed to the CO2-TPEs via addition of a small amount of boronic ester as dynamic cross-linker. The mechanical properties in...

Construction of block copolymers is a practical method for modifying the properties of CO2-based polycarbonates (CO2-PCs) in order to meet specific needs. Herein, we report a well-defined single-site β-diiminate zinc complex 1 equipped with the capacities of coordination copolymerization of CO2/epoxide and reversible addition–fragmentation chain transfer (RAFT) polymerization of vinyl monomers. Complex 1 is specifically designed to possess a 3-(benzylthiocarbonothioylthio)propionate (BSTP) initiating group, which enables the controlled ring-opening copolymerization of epoxides and CO2, leaving a polycarbonate with BSTP functional group at the end of the chain. The end-capped BSTP allows direct chain extension via living RAFT polymerization, thus providing a robust method to construct various CO2-based block copolymers in one pot via a tandem catalysis strategy. The structure of 1 is established by single-crystal X-ray diffraction as well as 1H and 13C NMR. By utilizing 1, a wide range of CO2-based block c...

The coupling of epoxides and carbon dioxide to polycarbonates (CO2–PCs) has been the subject of intense research for nearly half a century. Although tremendous progress has been achieved, their aliphatic characteristics and lack of functionalities of CO2–PCs limit the scope of their application in high value-added and functional materials. In this article, the first CO2-based polycarbonate with the ability to autonomously self-heal is constructed via a one-pot synthetic strategy. The key to the success of the synthetic strategy is efficient tandem three different catalytic reactions, i.e., hydrolysis of epoxides, immortal copolymerization of CO2/epoxides, and thiol–ene click reactions in a one-pot process. Based on the standard tensile testing, these CO2-based materials show robust self-healing properties, where the extensibility, maximal strength, and Young’s modulus of the specimens can almost entirely recover to their original value under ambient temperature. Our studies demonstrate that the self-heali...

Bioinspired polyphenol/polyamine codeposition has been demonstrated by the competence for surface modification; however, the reaction processes including mechanism and kinetics remain superficially understood. In this work, the catechol (CA)-amine reaction has been thoroughly investigated by using CA and two amines m-phenylenediamine and piperazine. We verify that both primary and secondary amines are prone to link with CA through Michael addition to form polyphenol/polyamine oligomers under aerobic and mild-alkaline conditions. Molecular simulations indicate that the Michael addition products are dominant for both aromatic and aliphatic amines with CA, which supports the durable chem- and phystability of the codeposited coatings. The aggregation kinetics of polyphenol/polyamine is provided for the first time, and the formed aggregates show high-adhesive properties, which can be deposited as the skin layers for high-performance nanofiltration membranes.

Immortal copolymerization of epoxides/CO2 using macro-chain-transfer agent (macro-CTA) is a useful method to prepare CO2-based block copolymers for manufacturing high value-added materials. Despite a variety of CO2-based block copolymers that have been reported using distinct macro-CTAs, issues including catalytic activity and blocking efficiency for the immortal polymerization remain superficially understood. Here, we systematically studied the reaction activity and blocking efficiency by using various macro-CTAs (including PPG, PEG, and PS) in the presence of two classical catalyst systems ((BDI)ZnOAc and SalenCoTFA/PPN-TFA). By analysis of the gel permeation chromatograms via mathematical deconvolution, it comes to a conclusion that the size, nature, and ratio of [macro-CTA]/[Cat.] strongly influence the catalytic activity of the reaction and blocking efficiency for the resultant block copolymers. Thin film self-assembly of PS/PPC block copolymers was investigated, and the results were analyzed by SEM ...

Control over the orientation of cylindrical and lamellar domains is required for pattern transfer in block copolymer lithography. Previous work mainly focuses on the use of random copolymer brushes to control the wetting behaviors of block copolymers (BCPs), but random copolymerization is only limited to a few monomer pairs. Here we demonstrate the use of homopolymer brushes/mats to modify the substrate to form a chemically homogeneous surface. The surface affinity is tuned by changing the monomer substituent, and a variety of wetting behaviors are obtained in BCP films on homopolymer brushes/mats. Three series of hydroxy-terminated or cross-linkable homopolymers, including polymethacrylate, polyacrylate, and polystyrene derivatives, are prepared for controlling the BCP–substrate interaction. Both preferential and nonpreferential wetting behaviors of poly(styrene-b-methyl methacrylate), poly(styrene-b-rac-lactide), and poly(styrene-b-propylene carbonate) films are obtained as the homopolymer structures ch...

Porous separators are key components for lithium-ion batteries (LIBs) and they have drawn considerable attention because of their vital role in governing battery cost and performance (e.g., power density, safety, and longevity). Here, zirconia-coated separators were fabricated via a facile biomineralization process with the aim to improve the performance of commercialized polypropylene separators. The as-prepared organic-inorganic composite separators show excellent thermal stability, even at the melting temperature (160 °C) of polypropylene. This is due to the well-distributed zirconia coatings on the separator surfaces. Furthermore, the interfacial impedance of the composite separators is only 343.8 Ω, which is four times lower than the pristine polypropylene ones. The results demonstrate an attractive method to prepare organic-inorganic composite separators with outstanding properties, which makes them promising candidates for high-performance LIBs.

A Janus membrane with opposing wettability was first reported with both function of water-to-oil and oil-to-water emulsification. This membrane is conveniently fabricated by single-surface deposition of polydopamine/polyethylenimine (PDA/PEI). The asymmetric wettability can also reduce the transmembrane resistance during the process, indicating an economical and promising strategy to prepare various emulsions. This research opens a novel avenue for exploring and understanding the Janus membrane, and provides a perspective to design the asymmetric membrane structures with promoted performance in conventional membrane processes.

Directed self-assembly (DSA) of block copolymers (BCPs) combines advantages of conventional photolithography and polymeric materials and shows competence in semiconductors and data storage applications. Driven by the more integrated, much smaller and higher performance of the electronics, however, the industry standard polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) in DSA strategy cannot meet the rapid development of lithography technology because its intrinsic limited Flory–Huggins interaction parameter (χ). Despite hundreds of block copolymers have been developed, these BCPs systems are usually subject to a trade-off between high χ and thermal treatment, resulting in incompatibility with the current nanomanufacturing fab processes. Here we discover that polystyrene-b-poly(propylene carbonate) (PS-b-PPC) is well qualified to fill key positions on DSA strategy for the next-generation lithography. The estimated χ-value for PS-b-PPC is 0.079, that is, two times greater than PS-b-PMMA (χ = 0.029 at ...

Block copolymer electrolytes (BCEs) represent an attractive choice as solid-state ionic conductors for electrochemical technologies used in energy storage and conversion, water treatment, sensors, and data storage and processing. Unlocking the maximum ionic conductivity of BCEs requires an intimate understanding as to how the microphase separated structure influences transport properties. However, elucidating such knowledge remains elusive due to the challenging task of precisely engineering BCEs with a defined structure in bulk materials. In this work, we examined BCEs in a thin film format because it was amenable to attaining BCEs with a desired nanostructure. Specifically, we systematically investigated anion-conducting BCEs with different degrees of connectivity of the ionic domains. For the first time, we demonstrate that increasing terminal defects in the ionic domain from 1 terminal defect per μm2 to 20 terminal defects per μm2 (a relatively small amount of defects) decreased ionic conductivity by 67% compared to the maximum value attained. Conversely, maximizing ionic domain connectivity increased the ionic conductivity by two-fold over a non-ordered BCE film. These experiments highlight that microphase separation alone was insufficient for ameliorating ionic conductivity in BCEs. Rather, microphase separation coupled with complete ionic domain connectivity realized BCEs with significantly enhanced ionic conductivity.

Enhanced capabilities of stain removal and comfort control are simultaneously achieved by the light and thermo dual-responsive copolymer poly(triethylene glycol methyl ether methacrylate- co-ethylene glycol methacrylate- co-acrylamide azobenzene) (P(MEO3MA- co-EGMA- co-AAAB)) cross-linked on cotton fabrics. P(MEO3MA- co-EGMA- co-AAAB) is synthesized by sequential atom transfer radical polymerization with a molar ratio of 8 (MEO3MA):1 (EGMA):1 (AAAB). The MEO3MA units induce a thermoresponsive behavior to the copolymer. The hydrophilicity of the copolymer films can be further improved by the light-induced trans- cis isomerization of the AAAB units with UV radiation. The copolymer is facilely immobilized onto cotton fabrics with 1,2,3,4-butane tetracarboxylic acid as cross-linker. Due to the immobilization of P(MEO3MA- co-EGMA- co-AAAB), the hydrophilicity of the fabric surface is increased under UV radiation. Therefore, by simply installing a UV light source in the washing machine, better capability of stain removal is realized for the cross-linked cotton fabrics. It can prominently reduce the consumption of energy, water, and surfactants in laundry. In addition, the trans-AAAB units of the copolymer cause the cross-linked P(MEO3MA- co-EGMA- co-AAAB) layer to be more hydrophobic under ambient conditions. Hence, the copolymer can more easily collapse and form a porous structure on the fabrics. Thus, the air permeability of cotton fabrics cross-linked with P(MEO3MA- co-EGMA- co-AAAB) is enhanced by 13% at human body temperature as compared to P(MEO3MA- co-EGMA), giving improved comfort control during daily wear.

Homoporous membranes fabricated by self-assembled block copolymers (BCPs) have gained growing attention for their easy availability of well-ordered nanostructures for precise separation. However, it remains a challenges to improve the mechanical integrity, hydrophilic properties, and pore functionalities of the existing systems. To this end, we report an organic-mineral composite hybrid nanoporous BCP membrane with attractive superhydrophilicity, mechanical stability, and fouling-resistance derived from a bioinspired block copolymer, poly(propylene carbonate)- block-poly(4-vinylcatechol acetonide) (PPC- b-PVCA). The key advances include the following. (1) The PPC minor block is qualified as sacrificial domain because of its alkali sensitivity for generating monodisperse nanopores. (2) The PVCA matrix block contains the catechol groups, which enables the formation of inorganic layer via a biomineralization process, thus producing an organic-mineral composite nanoporous BCP membrane with attractive superhydrophilicity, mechanical stability, and fouling resistance. A ∼200 nm thickness BCP film with monodisperse through-pores of 12 nm diameter cylinders oriented perpendicularly to a supporting microfiltration membrane is fabricated by sequential blade-casting, solvent annealing, hydrolysis sacrificial block, and biomineralization process. The mechanical stability, high water flow (114 L m

The addition of water as a chain transfer reagent during the copolymerization reaction of epoxides and carbon dioxide has been shown as a promising method for producing CO2-based polycarbonate polyols. These polyols can serve as drop-in replacements for petroleum derived polyols for polyurethane production or designer block copolymers. Ironically, during the history of CO2/epoxide coupling development, water was generally considered primarily as an aversion reagent. That is, in its presence, low catalytic activity and high polydispersity was normally observed. Recently, we reported a water-mediated tandem metal-coordination CO2/epoxide copolymerization and organobase catalyzed ring-opening polymerization (ROP) approach for the one-pot synthesis of an ABA CO2-based triblock copolymers. As in previous studies, water was deemed as the chain transfer reagent in this tandem strategy for producing CO2-based polyols. Herein is presented a mechanistic study aimed at determining the intimate role water plays durin...

Control over nanopore size and 3D structure is necessary to advance membrane performance in ubiquitous separation devices. Here, inorganic nanoporous membranes are fabricated by combining the assembly of cylinder-forming poly(styrene-block-methyl methacrylate) (PS-b-PMMA) block copolymer and sequential infiltration synthesis (SIS). A key advance relates to the use of PMMA majority block copolymer films and the optimization of thermal annealing temperature and substrate chemistry to achieve through-film vertical PS cylinders. The resulting morphology allows for direct fabrication of nanoporous AlOx by selective growth of Al2O3 in the PMMA matrix during the SIS process, followed by polymer removal using oxygen plasma. Control over the pore diameter is achieved by varying the number of Al2O3 growth cycles, leading to pore size reduction from 21 to 16 nm. 3D characterization, using scanning transmission electron microscopy tomography, reveals that the AlOx channels are continuous through the film and have a gradual increase in pore size with depth. Finally, the ultrafiltration performance of the fabricated AlOx membrane for protein separation as a function of protein size and charge is demonstrated.

Membrane fouling is one of the most severe problems restricting membrane separation technology for wastewater treatment. This work reports a photocatalytic nanofiltration membrane (NFM) with self-cleaning property fabricated using a facile biomimetic mineralization process. In this strategy, a polydopamine (PDA)/polyethyleneimine (PEI) intermediate layer is fabricated on an ultrafiltration membrane via a co-deposition method followed by mineralization of a photocatalytic layer consisting of β-FeOOH nanorods. The PDA–PEI layer acts both as a nanofiltration selective layer and an intermediate layer for anchoring the β-FeOOH nanorods via strong coordination complexes between Fe3+ and catechol groups. In visible light, the β-FeOOH layer exhibits efficient photocatalytic activity for degrading dyes through the photo-Fenton reaction in the presence of hydrogen peroxide, endowing the NFM concurrently with effective nanofiltration performance and self-cleaning capability. Moreover, the mineralized NFMs exhibit satisfactory stability under simultaneous filtration and photocatalysis processing, showing great potential in advanced wastewater treatment.