Conventional Polymerization Research Articles

Polymerization of Sodium 4-Styrenesulfonate Inside Filter Paper via Dielectric Barrier Discharge Plasma

This work explores the polymerization of sodium 4-styrenesulfonate (NaSS) inside filter paper using dielectric barrier discharge (DBD) plasma and its application in the environmental field. The plasma-based technique, performed under mild conditions, solves common problems associated with conventional polymerization inside porous materials. The polymerization process was monitored using Fourier-transform infrared (FTIR) spectroscopy, which confirmed the consumption of double bonds, particularly in NaSS samples containing the optimal concentration of crosslinker divinyl benzene (DVB) (0.25% wt). Our work demonstrates the effectiveness and promise of DBD plasma as a substitute polymerization approach, especially for those in porous materials.

Modulating low-temperature interfacial polymerization with NaHCO3 for high-performance ultrathin nanofiltration membranes

Conventional interfacial polymerization (IP) encounters significant challenges in achieving the desired nanofiltration (NF) membrane structure, owing to uncontrolled diffusion and ultrafast polymerization. Our study introduced carbonates into the low-temperature interfacial polymerization (LTIP) process to precisely regulate the diffusion of amine monomers and polymerization kinetics. Carbonates in the aqueous phase restrict the diffusion of amine monomers while promoting the generation of nanobubbles. Further utilization of the low-temperature oil phase not only retards polymerization but also facilitates the formation of foam nanostructures in the polyamide layer. Density functional theory calculations and molecular dynamics simulations revealed the mechanisms underlying the regulation of amine monomer diffusion and gas-bubble release by carbonates and LTIP. The fabricated membrane has a smoother, ultrathin separation layer while maintaining a high permeability of 35.0 L·m−2·h−1·bar−1 (nearly doubled compared with the pristine membrane) and high Na2SO4 rejection of 99.5 %. This study confirms the practicality of the carbonate-modulated LTIP strategy.

Comparison of the Antimicrobial Efficacy of Conventional Versus Chitosan Re-inforced Heat-Polymerized Polymethylmethacrylate Dental Material: An In Vitro Study.

Polymethylmethacrylate (PMMA) is widely used in the fabrication of dentures due to its aesthetic appeal and mechanical strength. However, PMMA's susceptibility to microbial colonization often leads to oral infections such as denture stomatitis. Enhancing the antimicrobial properties of denture materials is crucial for improving patient outcomes.Chitosan, a natural biopolymer, possesses inherent antimicrobial properties and could potentially enhance the microbial resistance of PMMA. This study has investigated thepotential of chitosan-reinforced heat-polymerized PMMA denture material to reduce microbial colonization. The aim of the study was to evaluate and assess the anti-bacterial and antifungal properties of chitosan-reinforced heat-polymerized PMMA with conventional heat-polymerized PMMA Materials and methods:Chitosan-reinforced PMMA samples were fabricated with varying chitosan concentrations (0% control, 5%, 10%, and 15% by weight). The fabrication involved mixing chitosan powder with PMMA powder, adding monomer liquid, followed by mixing, packing, and curing using the conventional heat polymerization technique. The antimicrobial efficacy was assessed in vitro using two common oral pathogens: Streptococcus mutans and Candida albicans. Blood agar plates were used for S. mutans and Sabouraud agar plates were used for C. albicans. Each sample was placed on the respective agar plates inoculated with a standardized microbial suspension and incubated at 37°C for 24 hours. The number of colony-forming units (CFUs) was counted to quantify microbial growth. Statistical analyses, including linear regression analysis, one-way ANOVA test, and Pearson correlation were performed to evaluate the relationship between chitosan concentration and antimicrobial efficacy. The p-value was calculated to determine the statistical significance of the results. The chitosan-reinforced PMMA samples showed significantly greater antimicrobial efficacy compared to the conventional PMMA samples. The CFU counts for both S. mutans and C. albicans decreased with increasing chitosan concentration. Linear regression analysis indicated a strong negative correlation between chitosan concentration and CFU counts, with Pearson correlation coefficients of -0.97 for S. mutans and -0.98 for C. albicans. ANOVA analysis revealed a statistically significant difference in antimicrobial efficacy across different chitosan concentrations (p < 0.001). Incorporating chitosan into heat-polymerized PMMA significantly enhances its antimicrobial properties against S. mutans and C. albicans. The antimicrobial efficacy improves with higher concentrations of chitosan, with the 15% chitosan-reinforced samples showing the most substantial reduction in microbial growth. These results suggest that chitosan-reinforced PMMA dentures could be a superior alternative to conventional PMMA dentures, potentially reducing denture-related infections and improving oral health outcomes for denture wearers.

Silver-π Interaction: A Diverse Approach to Hybrid Material and Its Efficacy in Electrocatalytic Reduction of Nitrate to Ammonia.

Inspired by the intriguing nature of the metal-π interaction in organometallic chemistry, a novel 1D hybrid material has been designed. Herein, a functionalized tellurium allyl macrocycle (TAM) acts as a molecular building block and is knit together via silver-π interaction to obtain Ag-TAM. Ag is coordinated to two allyl groups and a phenyl ring in η2 mode. Instead of the conventional polymerization strategy, a metal-π interaction is employed to interlink macrocycles. TAM and Ag-TAM showed electrocatalytic capability for the conversion of nitrate to ammonia. Ag-TAM showed an NH3 yield rate 2-fold greater than TAM with a high faradaic efficiency of 94.6% with good durability, proving that interlinking of macrocycles via metal-π interaction improves the catalytic activity. Detailed periodic density functional theory (DFT) calculations unveil novel mechanistic insights, suggesting cooperative catalysis between neighboring Ag sites and contributing to the enhanced efficiency.

Monomer elution and shrinkage stress analysis of addition-fragmentation chain-transfer-modified resin composites in relation to the curing protocol

ObjectiveThe purpose was to compare the effects of rapid (3 s) and conventional (20 s) polymerization protocols (PP) of mono- and multichip LED curing units (LCU) on shrinkage stress (SS) and monomer elution (ME) in bulk-fill resin-based composites (RBC) with and without addition-fragmentation chain-transfer (AFCT) monomer. MethodsCylindrical (5x4mm) specimens were prepared from two RBCs containing different AFCT monomers (Filtek OneBulk-FOB; Tetric PowerFill-TPF) and one without (Tetric EvoCeram Bulk-TEC). After soaking for 3, 10, and 14 days (75 % ethanol), ME was quantified using standard monomers by High-Performance Liquid Chromatography. SS was measured from the start of polymerization to 5 min using a Materials Testing Machine. The radiant exitance of LCUs was measured using a spectrophotometer. ANOVA and Tukey's post-hoc test, multivariate analysis and partial eta-squared statistics were used to analyze the data (p < 0.05). ResultsAFCT-modification significantly decreased ME (p < 0.001). ME was reduced by half by day 10 and by one tenth by the end of the 14-day compared to the 3-day sampling. ME itself was dependent, whereas the percentage of monomers released was independent of the PP used (p > 0.05). FOB showed the lowest SS (p < 0.001), while there was no significant difference between TPF and TEC (p = 0.124). Both ME and SS were significantly influenced by material type and PP. SignificanceThe incorporation of the AFCT monomer reduced ME, but this was inversely related to a decrease in exposure time. SS values reduced by rapid PP in parallel with increasing ME values. The utilization of the AFCT molecule in conjunction with an appropriate resin-, initiator-system is of significant consequence for the kinetics of polymerization and the incorporation of monomers into the network.

Mechanochemically Promoted Functionalization of Postconsumer Poly(Methyl Methacrylate) and Poly(α‐Methylstyrene) for Bulk Depolymerization

We describe a methodology of post‐polymerization functionalization to enable subsequent bulk depolymerization to monomer by utilizing mechanochemical macro‐radical generation. By harnessing ultrasonic chain‐scission in the presence of N‐hydroxyphthalimide methacrylate (PhthMA), we successfully chain‐end functionalize polymers to promote subsequent depolymerization in bulk, achieving up to 81% depolymerization of poly(methyl methacrylate) (PMMA) and poly(α‐methylstyrene) (PAMS) within 30 min. This method of depolymerization yields a high‐purity monomer that can be repolymerized. Moreover, as compared to the most common methods of depolymerization, this work is most efficient with ultra‐high molecular weight (UHMW) polymers, establishing a method with the potential to address highly persistent, non‐degradable all‐carbon backbone plastic materials. Lastly, we demonstrate the expansion of this depolymerization method to commercial cell cast PMMA, achieving high degrees of depolymerization from post‐consumer waste. This work is the first demonstration of applying PhthMA‐promoted depolymerization strategies in homopolymer PMMA and PAMS prepared by conventional polymerization methods.

Mechanochemically Promoted Functionalization of Postconsumer Poly(Methyl Methacrylate) and Poly(α-Methylstyrene) for Bulk Depolymerization.

We describe a methodology of post-polymerization functionalization to enable subsequent bulk depolymerization to monomer by utilizing mechanochemical macro-radical generation. By harnessing ultrasonic chain-scission in the presence of N-hydroxyphthalimide methacrylate (PhthMA), we successfully chain-end functionalize polymers to promote subsequent depolymerization in bulk, achieving up to 81% depolymerization of poly(methyl methacrylate) (PMMA) and poly(α-methylstyrene) (PAMS) within 30 min. This method of depolymerization yields a high-purity monomer that can be repolymerized. Moreover, as compared to the most common methods of depolymerization, this work is most efficient with ultra-high molecular weight (UHMW) polymers, establishing a method with the potential to address highly persistent, non-degradable all-carbon backbone plastic materials. Lastly, we demonstrate the expansion of this depolymerization method to commercial cell cast PMMA, achieving high degrees of depolymerization from post-consumer waste. This work is the first demonstration of applying PhthMA-promoted depolymerization strategies in homopolymer PMMA and PAMS prepared by conventional polymerization methods.

Organic-organic interfacial polymerization for the ultrathin polyamide organic solvent nanofiltration membranes

There is an increasing demand for advanced membranes that exhibit both high perm-selectivity and good stability in organic solvents, particularly for organic solvent nanofiltration (OSN). Traditional methods of synthesizing thin films using conventional interfacial polymerization (CIP) have been limited by the use of water-soluble monomers, which has hindered the development of high-performance membranes. To address this issue, a new method called organic-organic interfacial polymerization (OOIP) has been proposed. This method allows for the use of aromatic amines that are not water-soluble in the fabrication of ultrathin polyamide (PA) (<40 nm) thin film composite (TFC) membranes. By investigating five different organic solvents (tetrahydrofuran, acetone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide) with varying water content as the organic phase for a water-insoluble benzidine monomer, two diffusion models of monomers were identified that resulted in different membrane structures and degrees of network crosslinking. The ultrathin PA membranes produced using tetrahydrofuran-H2O and N,N-dimethylformamide-H2O, along with solvent activation, demonstrated high methanol permeances of 11.4 L m−2 h−1 bar−1 and 6.0 L m−2 h−1 bar−1, respectively, while maintaining exceptional rejections of over 99.0 % for small molecules with molecular weights greater than 452 g mol−1. The OOIP method is scalable and reproducible, making it suitable for large-scale membrane production. This innovative approach shows great potential for advancing OSN technology and providing efficient and cost-effective separation solutions for various industries.

An Innovative Approach for Tailoring Molecularly Imprinted Polymers for Biosensors-Application to Cancer Antigen 15-3.

This work presents a novel approach for tailoring molecularly imprinted polymers (MIPs) with a preliminary stage of atom transfer radical polymerization (ATRP), for a more precise definition of the imprinted cavity. A well-defined copolymer of acrylamide and N,N'-methylenebisacrylamide (PAAm-co-PMBAm) was synthesized by ATRP and applied to gold electrodes with the template, followed by a crosslinking reaction. The template was removed from the polymer matrix by enzymatic/chemical action. The surface modifications were monitored via electrochemical impedance spectroscopy (EIS), having the MIP polymer as a non-conducting film designed with affinity sites for CA15-3. The resulting biosensor exhibited a linear response to CA15-3 log concentrations from 0.001 to 100 U/mL in PBS or in diluted fetal bovine serum (1000×) in PBS. Compared to the polyacrylamide (PAAm) MIP from conventional free-radical polymerization, the ATRP-based MIP extended the biosensor's dynamic linear range 10-fold, improving low concentration detection, and enhanced the signal reproducibility across units. The biosensor demonstrated good sensitivity and selectivity. Overall, the work described confirmed that the process of radical polymerization to build an MIP material influences the detection capacity for the target substance and the reproducibility among different biosensor units. Extending this approach to other cancer biomarkers, the methodology presented could open doors to a new generation of MIP-based biosensors for point-of-care disease diagnosis.

A sub-10 nm polyamide nanofiltration membrane from polyvinylpyrrolidone-mediated interfacial polymerization

In conventional interfacial polymerization (IP) for thin-film composite nanofiltration membranes, the separation layer is typically thick (∼100 nm), which limits its water permeance. In this study, we successfully synthesized an ultrathin polyamide layer (∼8.6 nm) from polyvinylpyrrolidone (PVP)-mediated IP. With the surfactant concentration over its critical micelle concentration, PVP not only formed a monolayer at the water-heptane interface, but also stayed in the aqueous solution. The CO groups of PVP formed the N–H⋯O hydrogen bond interactions with N–H bonds of piperazine (PIP) monomers in the aqueous phase to slow down the diffusion of PIP monomers. Besides, PVP with amphiphilic groups minimized the interfacial tension at the water-heptane interface to regulate IP processes. By adjusting the concentration of PVP, we obtained a sub-10 nm polyamide nanofiltration membrane. Moreover, hydrophilic PVP macromolecules improved the membrane surface hydrophilicity. Due to the ultrathin thickness and improved hydrophilicity, the optimized polyamide membrane demonstrated a threefold increase in permeance compared to that of the pristine polyamide membrane without PVP addition, and maintained 98.4% rejection for 1000 ppm Na2SO4 solution. This study provides a new insight into fabricating sub-10 nm polyamide membranes for nanofiltration processes.

Ultrahighly Li-selective nanofiltration membranes prepared via tailored interfacial polymerization

Nanofiltration (NF) membrane-based separation has gained significant attention as an efficient technology for recovering lithium (Li) from salt-lake brines. However, many previously developed NF membranes are not commercially feasible because they lack sufficient Li selectivity and require the use of new monomers/chemicals or complicated fabrication processes. Herein, we propose a commercially viable method to fabricate ultrahighly Li-selective polyamide (PA) membranes by carefully tailoring a conventional interfacial polymerization process using an established piperazine (PIP)/trimesoyl chloride monomer system. The use of excess PIP endowed the fabricated membrane with enhanced PA crosslinking density and a positive surface charge, reinforcing both its size and Donnan exclusion mechanisms. Furthermore, the addition of benzyltributylammonium chloride, a cationic surfactant, to the PIP solution effectively improved the water permeance of the membrane without impairing its magnesium ion (Mg2+) rejection by loosening its PA network while enhancing its positive surface charge. Consequently, our tailor-made PA membranes with the proper pore structures and strong positive surface charges exhibited ultrahigh Li+/Mg2+ selectivity of up to 150 (under single-salt conditions) and 887 (under mixed-salt conditions), significantly outperforming commercial and other reported laboratory-made NF membranes. Our strategy provides a facile and effective means to manufacture Li-selective membranes with high commercial viability.

Precisely Controlled Polymerization of Two-Dimensional Conducting Polymers in Quasi-Liquid Layer Enables Ultrahigh Sensing Performance.

Gas sensors based on conducting polymers offer great potential for high-performance room temperature applications due to their cost-effectiveness, high-sensitivity, and operational advantage. However, their current performance is limited by the deficiency of control in conventional polymerization methods, leading to poor crystallinity and inconsistent material properties. Here, the quasi-liquid layer (QLL) on the ice surface acts as a self-regulating nano-reactor for precise control of thermodynamics and kinetics in the polymerization, resulting in a 7.62nm thick two-dimensional (2D) polyaniline (PANI) film matching the QLL thickness. The ultra-thin film optimizes the exposure of active sites, enhancing the detection of analyte gases at low concentrations. It is validated by fabricating a chemiresistive gas sensor with the 2D PANI film, demonstrating stable room-temperature detection of ammonia down to 10 ppt in ambient air with an impressive 10% response. This achievement represents the highest sensitivity among sensors of this kind while maintaining excellent selectivity and repeatability. Moreover, the QLL-controlled polymerization strategy offers an alternative route for precise control of the polymerization process for conducting polymers, enabling the creation of advanced materials with enhanced properties.

Well-defined star (co)polypeptides via a fast, efficient, and metal-free strategy

Polypeptides, especially star polypeptides, as a unique kind of biological macromolecules have broad applications in biomedical fields such as drug release, gene delivery, tissue engineering, and regenerative medicines due to their close structural similarity to naturally occurring peptides and proteins, biocompatibility, and amino acid functionality. However, the synthesis of star polypeptide mainly relies on the conventional primary amine-initiated ring-opening polymerization (ROP) of N-carboxyanhydrides (NCA) and suffers from low polymerization activity and limited controllability. This study proposes a fast, efficient and metal-free strategy to access star (co)polypeptides by combining the Michael reaction between acrylates and secondary aminoalcohols with the hydrogen-bonding organocatalytic ROP of NCA. This approach enables the preparation of a library of star (co)polypeptides with predesigned molecular weights, narrow molecular weight distributions, tunable arm number, and arm compositions. Importantly, this method exhibits high activity and selectivity at room temperature, making it both practical and versatile in synthesis applications.

Recent Developments on Cationic Polymerization of Vinyl Ethers.

In recent times, the evolution of cationic polymerization has taken a multidirectional approach, with the development of cationic reversible addition-fragmentation chain transfer (RAFT) polymerization. In contrast to the conventional cationic polymerization methods, which were typically carried out under inert atmospheres and low temperatures, various novel polymerization techniques have been developed where the reactions are carried out in open air, operate at room temperature, are cost-effective, and are environmentally friendly. Besides, several external stimuli, such as heat, light, chemicals, electrical potential, etc. have been employed to activate and control the polymerization process. It also enables the combination of cationic polymerization with other polymerization methods in a single reaction vessel, eliminating the necessity for isolation and purification during intermediate steps. In addition, significant advancements have been made through various modifications in catalyst systems, resulting in polymers with an exceptionally high level of stereoregularity. This review article comprehensively analyses the recent developments in cationic polymerization, encompassing their applications and offering insights into future perspectives.

Redox cationic frontal polymerization: a rapid curing approach for carbon fiber-reinforced composites with high fiber content

Conventional frontal polymerization processes for epoxy-based composites rely on cations and radicals generated by a short (and local) light or heat stimulus in the presence of an iodonium salt and a radical thermal initiator. However, due to heat losses, the propagation of the exothermic curing front is often limited by sample geometry and filler concentration. Redox cationic frontal polymerization (RCFP) is a promising approach to radically expand the composition and design options of frontally cured epoxy-based composites. By adding stannous octoate as reducing agent, a higher number of radicals and cations are generated at lower temperature, which yields highly cured composite even at elevated filler content. In the current study, RCFP was used to cure standard unidirectional carbon fiber-reinforced composites based on a commercially available epoxy resin and the properties were compared with its anhydride hardener-cured counterpart. Cure degree and thermal properties of the resins were determined by ATR FT-IR spectroscopy and DMA analysis. Subsequently, unidirectional composites with a fiber volume content of ~ 60% were produced via vacuum infusion and subjected to DMA, tensile, compression, and inter-laminar shear tests. The results showed a remarkable similarity between mechanical properties of RCFP and anhydride hardener-cured composites. The RCFP-cured composites exhibited even a higher damping resistance and compression strength than anhydride hardener-cured composites. The results show that RCFP allows for a significant reduction in the curing time (from several hours to 60 min), while it yields composites with properties comparable to classic anhydride-cured systems.Graphical abstract

Facile Synthesis of High Molecular Weight Poly(ethylene glycol)-b-poly(amino acid)s by Relay Polymerization.

Poly(amino acid)s (PAAs) are one kind of favorable biopolymer that can be used as a drug or gene carrier. However, conventional ring-opening polymerization of PAAs is slow and needs a strict anhydrous environment with an anhydrous reagent as well as the product without enough high molecular weight (Mn), which limits the expanding of PAAs' application. Herein, we took BLG-NCA as the monomer to quickly synthesize one kind of high Mn amphiphilic copolymer, poly(ethylene glycol)-b-poly(γ-benzyl-l-glutamic acid) (PEG-PBLG), by relay polymerization with a simple one-pot method within 3 h in mild conditions (open air, moisture insensitive). In the polymerization process, ring-opening polymerization-induced self-assembly in sodium bicarbonate aqueous solution first occurred to obtain low Mn PEG-PBLG seeds without purification. Then γ-benzyl-l-glutamate N-carboxyanhydride (BLG-NCA) dichloromethane solution was added into PEG-PBLG seeds directly and stirred vigorously to form am emulsion; during this process, the amphiphilic PEG-PBLG seeds will anchor on the interface of DCM and water to ensure the concentration of α-helix rigid PBLG in DCM to maintain the following relay polymerization. Then, high Mn PEG-PBLG was obtained in mild conditions in one pot. We found that the α-helix rigid structure was essential for relay polymerization by studying the synthetic speed of amphiphilic copolymer with different secondary structures. MOE simulation results showed that PBLG and BLG-NCA tended to form a double hydrogen bond, which was beneficial to relay polymerization because of higher local concentrations that can produce more double hydrogen bonds. Our strategy can quickly obtain high Mn PEG-PBLG (224.9 KDa) within 3 h from PEG-NH2 and BLG-NCA in one pot and did not need an extra initiator. After deprotection, the poly(ethylene glycol)-b-poly(l-glutamate acid) (PEG-PGA) with high Mn as a second product can be used as an excellent antitumor drug carrier. The high Mn PEG-PGA can achieve an encapsulation rate of 86.7% and a drug loading rate of 47.3%, which is twice that of the low Mn PEG-PGA. As a result, the synthesis of PEG-PBLG by relay polymerization simplified the process of PEG-PAA polymerization and increased the Mn. In addition, this method opened a way to obtain other kinds of high Mn PEG-PBLG values in the future.

A novel high temperature resistance thin film composite polyamide reverse osmosis membrane with covalent organic frameworks intermediate layer

Both salt rejection and pressure-bearing properties of the conventional thin film composite (TFC) polyamide reverse osmosis (RO) membrane are easily weakened at high temperature. In order to improve the high temperature resistance, in this work, a polyamide TFC RO membrane with covalent organic frameworks (COFs) intermediate layer was prepared. Firstly, the COFs layer was decorated on polyether sulfone (PES) support membrane by a unidirectional diffusion method and further modified for shrinking the micropore via the chemical crosslinking reaction with 1,3-diamino-2-propanol (DAPL) or ethylenediamine (EDA), and then continued the conventional interfacial polymerization of m-phenylene diamine (MPD) and trimesoyl chloride (TMC) on the resultant COFs layer for preparing the RO membrane. Furthermore, the correlationship between the microstructure of COFs layer and the separation performance of modified RO membrane was systematically investigated. Due to the introduction of the COFTpPa-DAPL intermediate layer with more regular microstructure and specific hydrophilicity, the resultant TFC-COFTpPa-DAPL RO membrane exhibited improvement in water flux by 30 ​% (reached to 50.5 ​L ​m−2 ​h−1) and higher salt rejection (>99.5 ​%) as compared with the conventional polyamide RO membrane and other reported temperature resistance RO membranes. Meanwhile, this TFC-COFTpPa-DAPL membrane showed good long-term separation stability during the RO process for 160 ​h. Especially, its water flux increased to 98.8 ​L ​m−2 ​h−1 without weakening salt rejection (about 99.4 ​%) at 70 ​°C. This study provides an effective way to fabricate the high temperature resistance TFC polyamide RO membrane with good comprehensive separation performance based on COFs intermediate layer.

Highly selective Mg2+/Li+ separation membranes prepared by surface grafting of a novel quaternary ammonium bromide

The efficient separation of Mg2+ and Li+ is the crucial step in the process of extracting lithium from salt lake brine. Nanofiltration (NF) membranes exhibit promising application potential in Mg2+/Li+ separation but the Mg2+/Li+ selectively of negatively charged NF membranes prepared by conventional interfacial polymerization process is far from desirable. In this study, a novel positively charged quaternary ammonium bromide, 3-bromopropyl trimethylammonium bromide (BTAB), is grafted on the polyethyleneimine (PEI)/trimesoyl chloride (TMC) NF membrane surface. This is achieved by a chemical reaction known as nucleophilic substitution, which involves the replacement of a bromine atom (-Br) with an amine group. Owing to the enhanced Donnan effects, the BTAB-modified NF membranes exhibit a MgCl2 rejection of up to 99.2 %, while maintaining a water flux of approximately 50 LMH under 5 bar. Meanwhile, the LiCl rejection is only ∼ 30 %. The Mg2+/Li+ selectively of the BTAB-modified NF membranes reaches 95.9 when filtrating a simulated brine with a Mg2+/Li+ ratio of 20 (2000 ppm MgCl2 and LiCl mixture), which is a twofold improvement compared with the pristine NF membranes. The working stability of the BTAB-modified NF membranes is confirmed by a 50-h continuous operation process. A two-stage NF treatment is conducted using a simulated East Taijinar salt lake brine, achieving Li2CO3 powder with a purity level of 99.4 %. The nucleophilic substitution reaction between -Br and the amine groups offers a good reference for the surface functionalization of NF membranes.

Constructing nanofiltration membrane on hydrophobic PVDF and PTFE substrates via reverse interfacial polymerization

Polyvinylidene fluoride (PVDF) and polytetrafluoroethylene(PTFE) porous membranes are ideal substrates for preparing thin-film composite (TFC) polyamide (PA) membranes with improved solvent resistance. However, it remains difficult to construct PA skin layers on PVDF and PTFE substrates via conventional interfacial polymerization (IP) due to the hydrophobic nature of these materials. To address this challenge, a reverse IP process was proposed to construct a defect-free PA skin layer on PVDF and PTFE substrates, in which the hydrophobic PVDF and PTFE substrates were soaked with the organic phase to ensure uniform coverage of reacted solution on the substrates. This novel strategy can effectively tackle the issue of uneven wetting of the aqueous phase on hydrophobic substrates in the conventional IP process. The resultant TFC membranes (i.e. Mrev-PVDF and Mrev-PTFE) exhibit excellent nanofiltration (NF) performance in both aqueous and organic solutions. Mrev-PVDF and Mrev-PTFE have MgCl2 rejections of 96.12% and 95.17%, alongside the water permeances of 12.8 LMH/bar and 11.2 LMH/bar, respectively (Mrev-PTFE was activated with DMF). It is further shown that Mrev-PVDF and Mrev-PTFE could also reject 99.4% and 98.5% of Congo red in methanol solution at solvent permeances of over 3.3 LMH/bar, while they also perform excellently in other polar protic solvents. Consequently, this work opens a new window for constructing high-performance TFC PA membranes on hydrophobic substrates and expands the application of the TFC PA NF membrane.

Thermoplastic polyurethane surface coated with polymer brushes for reduced protein and cell attachment.

The objective of this study was to coat negatively charged polymer brushes covalently onto the surface of thermoplastic polyurethane (TPU) using a simple conventional surface free-radical polymerization technique. The coated surfaces were assessed with contact angle, protein adsorption, cell adhesion and bacterial adhesion. Bovine serum albumin (BSA) and bovine fibrinogen (BFG) were used for protein adsorption evaluation. Mouse fibroblasts (NIH-3T3) and Pseudomonas aeruginosa (P. aeruginosa) were used to assess surface adhesion. Results show that the TPU surface modified with the attached polymer brushes exhibited significantly reduced contact angle, protein adsorption, and cell as well as bacterial adhesion, among which the negatively charged polymers showed the extremely low values in all the tests. Its contact angle is 5°, as compared to 70° for original TPU. Its BSA, BFG, 3T3 adhesion and P. aeruginosa adhesion were 93%, 84%, 92%, and 93% lower than original TPU. Furthermore, the TPU surface coated with negatively charged polymer brushes exhibited a hydrogel-like property. The results indicate that placing acrylic acids using a simple surface-initiated free-radical polymerization onto a TPU surface and then converting those to negative charges can be an effective and efficient route for fouling resistant applications.