Reducing active layer thickness of polyamide composite membranes using a covalent organic framework interlayer in interfacial polymerization

Polyamide(PA)-based thin-film composite membranes exhibit enormous potential in water purification,owing to their facile fabrication,decent performance and desirable stability.However,the thick PA active layer with high transport resistance from the conventional interfacial polymerization hampers their applications.The controllable fabrication of a thin PA active layer is essential for high separation efficiency but still challenging.Herein,a covalent organic framework TpPa-1 interlayer was firstly deposited on a polyethersulfone(PES)substrate to reduce the thickness of PA active layer in interfacial polymerization.The abundant pores of TpPa-1 increase the local concentration of amine monomers by adsorbing piperazine molecules,while hydrogen bonds between hydrophilic groups of TpPa-1 and piperazine molecules slow down their diffusion rate.Arising from those synergetic effects,the PA active layer is effectively reduced from 200 nm to 120 nm.By optimizing TpPa-1 interlayer and PA active layer,the water flux of resultant membranes can reach 171.35 L·m^-2·h^-1·MPa^-1,which increased by 125.4%compared with PA/PES membranes,while the rejection rates of sodium sulfate and dyes solution remained more than 90%and 99%,respectively.Our strategy may stimulate rational design of ultrathin PA-based nanofiltration membranes with high performances.

Preparation of Composite Charge-mosaic Hollow Fiber Membrane by Interfacial Polymerization

The preparation of composite charge-mosaic membrane included spinning of hollow fiber as the supporting membrane, preparing a selective layer on the inside surface of the fiber by interfacial polymerization. The charge-mosaic membranes show a high salt permeability while retaining sucrose. The charge-mosaic membrane can be effectively used to separate multivalent salts with organic matter of molecular weight great than 300 g/mol in industry.

CO2/CH4 separation using inside coated thin film composite hollow fiber membranes prepared by interfacial polymerization

Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was developed by interfacial polymerization between 1,3–cyclohexanebis–methylamine(CHMA) and trimesoyl chloride(TMC). ATR-FTIR, SEM and AFM were used to characterize the active thin layer formed inside the PSf hollow fiber. The separation behavior of the CHMA-TMC/PSf membrane was scrutinized by studying various effects like feed gas pressure and temperature. Furthermore, the influence of CHMA concentration and TMC concentration on membrane morphology and performance were investigated. As a result, it was found that mutually the CHMA concentration and TMC concentration play key roles in determining membrane morphology and performance. Moreover, the CHMA-TMC/PSf composite membrane showed good CO_2/CH_4 separation performance. For CO_2/CH_4 mixture gas(30/70 by volume) test, the membrane(PD1 prepared by CHMA 1.0% and TMC 0.5%) showed a CO_2 permeance of 25 GPU and the best CO_2/CH_4 selectivity of 28 at stage cut of 0.1. The high CO_2/CH_4 separation performance of CHMA-TMC/PSf thin film composite membrane was mostly accredited to the thin film thickness and the properties of binary amino groups.

Covalent organic frameworks-incorporated thin film composite membranes prepared by interfacial polymerization for efficient CO_(2) separation

Thin film composite(TFC)membranes with nanofillers additives for CO_(2)separation show promising applications in energy and environment-related fields.However,the poor compatibility between nanofillers and polymers in TFC membranes is the main problem.In this work,covalent organic frameworks(COFs,TpPa-1)with rich ANHA groups were incorporated into polyamide(PA)segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO_(2)/N_(2)separation.The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers,thereby enhancing compatibility.Besides,the incorporated COFs disturb the rigid structure of the PA layer,and provide fast CO_(2)transfer channels.The incorporated COFs also increase the content of effective carriers,which enhances the CO_(2)facilitated transport.Consequently,in CO_(2)/N_(2)mixed gas separation test,the optimal TFC(TpPa_(0.025)-PIP-TMC/m PSf)membrane exhibits high CO_(2)permeance of 854 GPU and high CO_(2)/N_(2)selectivity of 148 at 0.15 MPa,CO_(2)permeance of 456 GPU(gas permeation unit)and CO_(2)/N_(2)selectivity of 92 at 0.5 MPa.In addition,the Tp Pa_(0.025)-PIP-TMC/m PSf membrane also achieves high permselectivty in CO_(2)/CH_(4)mixed gas separation test.Finally,the optimal TFC membrane showes good stability in the simulated flue gas test,revealing the application potential for CO_(2)capture from flue gas.

Preparation of Thin Film Composite Nanofiltration Membrane by Interfacial Polymerization with 3,5-Diaminobenzoylpiperazine and Trimesoyl Chloride

A new aromatic diamine,3,5-diaminobenzoylpiperazine （3,5-DABP）,was synthesized from 3,5-diaminobenzoic acid and 1-formyl piperazine.The structure of 3,5-DABP was identified by FT-IR spectra and 1H NMR spectra.With 3,5-DABP as aqueous monomer and trimesoyl chloride （TMC） as organic monomer,thin film composite （TFC） nanofiltration membranes were prepared by interfacial polymerization technology.The salt rejection order of these TFC membranes is Na2SO4MgSO4MgCl2NaCl.This sequence indicates that the membranes are negatively charged.

Highly permeable reverse osmosis membranes incorporated with hydrophilic polymers of intrinsic microporosity via interfacial polymerization

Enhancing the water permeation while maintaining high salt rejection of existing reverse osmosis(RO)membranes remains a considerable challenge.Herein,we proposed to introduce polymer of intrinsic microporosity,PIM-1,into the selective layer of reverse osmosis membranes to break the trade-off effect between permeability and selectivity.A water-soluble a-LPIM-1 of low-molecular-weight and hydroxyl terminals was synthesized.These designed characteristics endowed it with high solubility and reactivity.Then it was mixed with m-phenylenediamine and together served as aqueous monomer to react with organic monomer of trimesoyl chloride via interfacial polymerization.The characterization results exhibited that more“nodule”rather than“leaf”structure formed on RO membrane surface,which indicated that the introduction of the high free-volume of a-LPIM-1 with three dimensional twisted and folded structure into the selective layer effectively caused the frustrated packing between polymer chains.In virtue of this effect,even with reduced surface roughness and unchanged layer thickness,the water permeability of prepared reverse osmosis membranes increased 2.1 times to 62.8 L·m^(-2)·h^(-1) with acceptable Na Cl rejection of 97.6%.This attempt developed a new strategy to break the trade-off effect faced by traditional polyamide reverse osmosis membranes.

Emulsion interfacial polymerization of anticancer peptides:fabricating polypeptide nanospheres with high drug-loading efficiency and enhanced anticancer activity

The development of drug delivery systems with high drug-loading efficiency, kinetic stability against dilution, as well as enhanced anticancer activity is of crucial importance to the fields of self-assembly and nanomedicine. Herein, we propose a strategy where the anticancer peptide acts as water-soluble monomer to directly participate in emulsion interfacial polymerization for fabricating polypeptide nanospheres. The constructed polypeptide nanospheres hold a high drug loading efficiency of 77%, and can be stably dispersed in highly diluted aqueous solutions. The acid-labile amide linkage in polypeptide nanospheres can be hydrolyzed in tumor acidic environments, thus releasing anticancer peptides selectively. The polypeptide nanospheres achieve significantly enhanced anticancer activity against HCT116 cells in vitro and in vivo through improved mitochondrial and membrane disruption. In addition, its side effects on normal cells can be reduced significantly. It is highly anticipated that more kinds of anticancer drug candidates or anticancer drugs can be applied to fabricate polymeric nanomedicines with improved anticancer activity through this strategy.

Epoxy microcapsules for high-performance self-healing materials using a novel method via integrating electrospraying and interfacial polymerization

The high-efficiency fabrication of high-quality microcapsules containing epoxy is crucial to the further development of the potential practical self-healing epoxy systems based on microencapsulated two-part epoxy-amine chemistry.Herein,a novel microencapsulation technique based on non-equilibrium droplets via integrating electrospraying and interfacial polymerization(ES-IP)was established to efficiently microencapsulate epoxy monomers.The ES-IP technique,consisting of three continuous steps,i.e.electrospraying to massively generate droplets,enwrapping every single droplet through instant interfacial polymerization,and thickening shell at an elevated temperature,has great flexibility to regulate the microencapsulation process and the microcapsule quality.The fabricated core-shell structured epoxy microcapsules(Ep-MCs)were comprehensively characterized for their properties,showing that they have high cleanness with rare impurities,controllable and tunable size,good thermal stability and tightness,and high effective core fraction.The high-quality Ep-MCs were adopted to formulate a self-healing epoxy based on the microencapsulated epoxy-amine chemistry.The highest healing efficiency,in terms of the recovered mode I fracture toughness,of 110±17%was achieved after being healed at room temperature(~25℃)for 48 h.While the developed ES-IP technique facilitates the microencapsulation technique based on non-equilibrium droplets,the fabricated high-quality Ep-MCs greatly promote the further developments of the practical self-healing materials.

Ultrathin Nanofilms Prepared by Interfacial Polymerization

Recently,Livingston and his colleagues published two articles in Nature and Science,respectively,to tackle the challenges of accurate molecular sieving and crude oil separation in the field of membrane separation by preparing ultrathin nanofilms through interfacial polymerization.One is that the nanofilms with ordered sub-nanopores achieve accurate molecular sieving atångström precision,and the other is that the permeability of hydrophobic polyamide nanofilms to hydrophobic liquid is significantly enhanced by an order of magnitude.The thoughtful design and excellent performance provide a feasible strategy for the development of membrane separation,and show great potential in industrial applications(drug separation and crude oil fractionation).

Polyamide Nanofiltration Membrane from Surfactant-assembly Regulated Interfacial Polymerization of 2-Methylpiperazine for Divalent Cations Removal

Removal of metal ions from water can not only alleviate the scaling problem of domestic and industrial water,but also solve the water safety problem caused by heavy metal ion pollution.Here,we fabricate a positively charged nanofiltration membrane via surfactant-assembly regulated interfacial polymerization(SARIP)of 2-methylpiperazine(MPIP)and trimesoyl chloride(TMC).Due to the existence of methyl substituent,MPIP has lower reactive activity than piperazine(PIP)but stronger affinity to hexane,resulting in a nanofiltration(NF)membrane with an opposite surface charge and a loose polyamide active layer.Interestingly,with the help of sodium dodecyl sulfate(SDS)assembly at the water/hexane,the reactivity between MPIP and TMC was obviously increased and caused in turn the formation of a positively charged polyamide active layer with a smaller pore size,as well as with a narrower pore size distribution.The resulting membrane shows a highly efficient removal of divalent cations from water,of which the rejections of MgCl_(2),CoCl_(2)and NiCl_(2)are higher than 98.8%,98.0%and 98.0%,respectively,which are better than those of most of other positively charged NF membranes reported in literatures.

Aqueous Two-Phase Interfacial Assembly of COF Membranes for Water Desalination

Aqueous two-phase system features with ultralow interfacial tension and thick interfacial region,affording unique confined space for membrane assembly.Here,for the first time,an aqueous two-phase interfacial assembly method is proposed to fabricate covalent organic framework(COF)membranes.The aqueous solution containing polyethylene glycol and dextran undergoes segregated phase separation into two water-rich phases.By respectively distributing aldehyde and amine monomers into two aqueous phases,a series of COF membranes are fabricated at water-water interface.The resultant membranes exhibit high NaCl rejection of 93.0-93.6% and water permeance reaching 1.7-3.7 L m^(−2) h^(−1) bar^(−1),superior to most water desalination membranes.Interestingly,the interfacial tension is found to have pronounced effect on membrane structures.The appropriate interfacial tension range(0.1-1.0 mN m^(−1))leads to the tight and intact COF membranes.Furthermore,the method is extended to the fabrication of other COF and metal-organic polymer membranes.This work is the first exploitation of fabricating membranes in all-aqueous system,confering a green and generic method for advanced membrane manufacturing.

Electrochemical performance of interfacially polymerized polyaniline nanofibres as electrode materials for non-aqueous redox supercapacitors

H+ doped polyaniline nanofibre(PH) was synthesized by interfacial polymerization and polyanilines doped with Li salt(PLI and PHLI) were prepared by immersing emeraldine base(EB) and H+ doped polyaniline in 1 mol/L LiPF6/(EC-EMC-DMC),respectively.PH,PLI and PHLI were all characterized by scanning electron microscopy(SEM) and Fourier transform infrared(FT-IR) spectrometry.With 1 mol/L LiPF6/(EC-EMC-DMC) as electrolyte,PH,PHLI and PLI were used as the active materials of symmetric non-aqueous redox supercapacitors.PLI shows the highest initial specific capacitance of 120 F/g(47 F/g for PH and 66 F/g for PHLI) among three samples.After 500 cycles,the specific capacitance of PLI remains 75 F/g,indicating the good cycleability.

Preparation of Poly-α-Olefin Microcapsule Particles Coated with Polyurethane as a Drag Reducer Based on Interface Polymerization

The molecular behavior of polyurethane(PU)coating materials during the surface adsorption of poly-α-olefin as a drag reducing polymer was explored by a molecular dynamics simulation.Three different PU capsule wall materials were synthesized using two reaction monomers,and a poly-α-olefin/PU drag reducer microcapsule was prepared based on interface polymerization.The structure,morphology,thermal stability,compressive strength,and drag reduction performance of the microcapsules were characterized and compared.The results showed that a non-bonding interaction induced the adsorption of the PU coating material,poly-α-olefin and PU then fused at the interface,and the PU coating material was embedded into the inner grooves of poly-α-olefin in the form of a local mosaic,thereby forming a stable core–shell structure.The morphological characterization indicated that PU and poly-α-olefin could form microcapsule structures.The thermal decomposition temperature of the microcapsule was dependent on the type of capsule wall material.The microcapsule structure had a slight effect on poly-α-olefin drag reduction.The system enabled poly-α-olefin to exist in powdered particles through microcapsulation,and had a good dispersion effect that facilitated storage and transport processes.The method effectively inhibited the accumulation and bonding of poly-α-olefin at room temperature.

Synthesis and Characterization of Ethylenediamine Tetraacetic Acid Tetrasodium Salt Loaded in Microcapsules with Slow Release Properties

The microcapsules with cores of ethylenediamine tetraacetic acid tetrasodium salt(Na4-EDTA)and walls of polyurea were synthesized via an interfacial polycondensation reaction with 2,4-tolylene diisocyanate as an oil-soluble monomer and diethyl triamine as a water-soluble monomer.Various manufacturing parameters,including the amount of emulsifier,agitation speed,stirring time and ratios of the wall materials to core materials,were altered to optimize process variables during the synthesis of microcapsules,and the effects of these parameters on the characteristics of the microcapsules were examined.The structure,morphology,mean particle size and size distribution were characterized by optical microscope and scanning electron microscopy(SEM),showing that the mean diameter of optimal microspheres was approximately 6μm,and microcapsules were spherical.In vitro release of Na4-EDTA from these microcapsules was performed in distilled water.Under the optimal preparation conditions, the Na4-EDTA release profiles were biphasic with a burst release followed by a gradual release phase.After an initial burst,a continuous Na4-EDTA release was up to 5-7 days.The optimal synthesis conditions for the microcapsules with stable,good morphology and good controlled-release properties were as follows:emulsifier Span-80 10% (by mass),agitation speed 900 r·min1,stirring time 30 min,and the ratio of the wall materials to core materials 0.15.

Substrate matters:The influences of substrate layers on the performances of thin-film composite reverse osmosis membranes

Thin-film composite(TFC) reverse osmosis(RO) membranes are playing the dominating role in desalination.Tremendous efforts have been put in the studies on the polyamide selective layers. However, the effect of the substrate layers is far less concerned. In this review, we summarize the works that consider the impacts of the substrates, including pore sizes, surface hydrophilicity, on the processes of interfacial polymerization and consequently on the morphologies of the active layers and on final RO performances of the composite membranes. All the works indicate that the pore sizes and surface hydrophilicity of the substrate evidently influence the RO performances of the composite membranes. Unfortunately, we find that the observations and understandings on the substrate effect are frequently varied from case to case because of the lack of substrates with uniform pores and surface chemistries. We suggest using track-etched membranes or anodized alumina membranes having relatively uniform pores and functionalizable pore walls as model substrates to elucidate the substrate effect.Moreover, we argue that homoporous membranes derived from block copolymers have the potential to be used as substrates for the large-scale production of high-performances TFC RO membranes.

Preparation and Characterization of a Novel Polyamide Charged Mosaic Membrane

A novel composite charged mosaic membrane(CCMM) was prepared via interfacial polymerization(IP) of polyamine[poly(epichlorohydrin amine) ]and trimesoyl chloride(TMC) on the polyethersulfone(PES) support. Fourier transform infrared spectroscopy(FT-IR) ,environmental scanning electron microscopy(ESEM) ,atomic force microscopy(AFM) and water contact angle analysis were applied to characterize the resulted CCMM.The FT-IR spectrum indicates that TMC reacts sufficiently with polyamine.ESEM and AFM pictures show that the IP process produces a dense selective layer on the support membrane.The water contact angle of the CCMM is smaller than that of the substrate membrane because of the cross-linked hydrophilic polyamine network.Several factors affecting the IP reaction and the performance of the CCMM,such as monomer concentration,reaction time,pH value of aqueous phase solution and post-treatment,were studied.The pure water flux of the optimized CCMM is 14.73 L·m -2 ·h -1 ·MPa -1 at the operating pressure of 0.4 MPa.The values of separation factorαfor NaCl/PEG1000/water and MgCl2/PEG1000/water are 11.89 and 9.96,respectively.These results demonstrate that CCMM is promising for the separation of low-molecular-weight organics from their salt aqueous solutions.

Preparation of Well-shaped Microcapsule Immobilizing Inorganic Nanoparticles

A facile and efficient method has been developed for microencapsulation of metal oxide nanoparticles in polyurea via interfacial polymerization of toluene-2,4-diisocyanate and H20 through the atomizing emulsification approach. The resultant microcapsules were well-shaped and uniform sphere with diameter ranging from 2 to 6 um. Thermogravimetry （TG） and differential scanning calorimetry （DSC） curves revealed that the microcapsules showed good thermal stability （no decomposition observed under 245℃）. Besides, the microencapsulated TiC2 has been used as an efficient catalyst for photocatalytic degradation of methyl orange. Furthermore, the photocatalysis of immobilized TiC2 could be enhanced by introducing UV absorbing agent to the wall of microcapsules.

Ferric acetylacetonate/covalent organic framework composite for high performance photocatalytic oxidation

Ferric acetylacetonate/covalent organic framework(Fe(acac)_(3)/COF)composite was synthesized by interfacial polymerization method at room temperature.The crystal structure,morphology and porosity property of the composite were characterized by X-ray diffraction,scanning electron microscope,transmission electron microscope and nitrogen adsorption.The interaction between Fe(acac)_(3) and COF was investigated by Fourier transform infrared spectra and X-ray photoelectron spectroscopy.The Fe(acac)_(3)/COF composite was used as a photocatalyst for the oxidation of benzyl alcohol under mild conditions.It exhibits high activity and selectivity for the reaction,of which the mechanism was investigated by determining its photoelectric properties.The Fe(acac)_(3)/COF catalyst developed in this work has application potential in other photocatalytic reactions.

Effects of Processing Conditions on the Properties of Epoxy Resin Microcapsule

In order to improve the healing performance and increase the service life of the polymer matrix composites, microcapsules were prepared by interracial polymerization process with urea formaldehyde resin and epoxy resin E-51 as the wall material and core material separately. The effects of core/shell mass ratio and emulsifier on the distribution, topography and encapsulation rate of microcapsules were investigated. By optimizing the conditions, microcapsules with little particle size, well dispersion and compact surface were prepared. The distribution, topography, stability and compositions of the microcapsules were characterized using Nano-2s, optical microscope, scanning electron microscopy, thermal analysis and Fourier transform infrared spectroscopy. The osmosis performance of the microcapsules was evaluated. The experimental results showed that the ratio of core/shell materials （1：1） and 1% DBS as emulsifier were optimum preparation conditions and the encapsulation rate was 62.5%. The microcapsules can be synthesized successfully with mean diameter 548.6 nm and exhibit a good chemical stability below 225 ℃. The FTIR result indicated that urea-formaldehyde resin was formed and the core materials were successfully encapsulated in urea-formaldehyde shell. Osmosis performance evaluation showed that the microcapsules were well coated and slowly osmosed.

Preparation and Characterization of Tri-channel Hollow Fiber Nanofiltration Membrane

Improvement strength is beneficial to the popularization of hollow fiber nanofiltration(NF) membrane.The tri-channel hollow fiber NF membrane was prepared by interfacial polymerization(IP).The high strength tri-channel hollow fiber ultrafiltration(UF) membrane were used as the support membrane,m-phenylenedianline(m-PDA),and polyethylenimine(PEI) were used as aqueous phase monomer,and trimesoyl chloride(TMC) was used as organic phase monomer.Fourier transform infrared spectroscopy(FTIR),scanning electron microscope(SEM),and gas sorption analyzer(GSA) were applied in structural analysis of NF membrane.Polymer FTIR illustrates the IP occurrence between aqueous phase monomer and organic phase monomer.The SEM images of NF membrane show the formation of a thin dense layer on surface of support membrane after IP.The flux(J) of optimal NF membrane is 11.2 L·m-2· h-1 at the 0.35 MPa operating pressure.Its retention(R) for NaCl,Na2SO4,MgCl2,Xylenol orange,and Neutral red is 17.4%,30.2%,16.1%,94.3%,and 51.0%,respectively.The NF membrane is on negative charge and its pore radius distributes between 0.3-2.0 nm.