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1.
Angew Chem Int Ed Engl ; 63(23): e202402509, 2024 06 03.
Artículo en Inglés | MEDLINE | ID: mdl-38588046

RESUMEN

Membranes are important in the pharmaceutical industry for the separation of antibiotics and salts. However, its widespread adoption has been hindered by limited control of the membrane microstructure (pore architecture and free-volume elements), separation threshold, scalability, and operational stability. In this study, 4,4',4'',4'''-methanetetrayltetrakis(benzene-1,2-diamine) (MTLB) as prepared as a molecular building block for fabricating thin-film composite membranes (TFCMs) via interfacial polymerization. The relatively large molecular size and rigid molecular structure of MTLB, along with its non-coplanar and distorted conformation, produced thin and defect-free selective layers (~27 nm) with ideal microporosities for antibiotic desalination. These structural advantages yielded an unprecedented high performance with a water permeance of 45.2 L m-2 h-1 bar-1 and efficient antibiotic desalination (NaCl/adriamycin selectivity of 422). We demonstrated the feasibility of the industrial scaling of the membrane into a spiral-wound module (with an effective area of 2.0 m2). This module exhibited long-term stability and performance that surpassed those of state-of-the-art membranes used for antibiotic desalination. This study provides a scientific reference for the development of high-performance TFCMs for water purification and desalination in the pharmaceutical industry.


Asunto(s)
Antibacterianos , Membranas Artificiales , Nylons , Antibacterianos/química , Antibacterianos/aislamiento & purificación , Nylons/química , Purificación del Agua/métodos , Filtración/métodos , Permeabilidad
2.
ACS Appl Mater Interfaces ; 16(1): 1451-1460, 2024 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-38112199

RESUMEN

Hydrogels with excellent mechanical flexibility are widely used in flexible electronic devices. However, it is difficult to meet further applications of high-power integrated flexible electronics as a result of their low thermal conductivity. Herein, highly thermally conductive composite hydrogels with a solid-liquid interpenetrating thermal conductivity network are constructed by aromatic polyamide nanofibers (ANF) and fluorinated graphene (FG) reinforced poly(vinyl alcohol) (PVA) and cross-linked by tannic acid (TA) solution immersion to obtain a hydrogel with a double cross-linked network. The PVA-ANF-FG3T-11.1% composite hydrogel exhibits good mechanical properties compared to PVA-ANFT, with a tensile modulus of up to 0.89 MPa, a tensile strength of up to 1.23 MPa, and an energy of rupture of up to 3.45 MJ cm-3, which is mainly attributed to the multihydrogen bonding interactions in the composite hydrogel. In addition, the friction coefficient of the PVA-ANF-FG3T-11.1% composite hydrogel is 0.178, making it suitable for use in high-friction coefficient applications. The thermal conductivity of the PVA-ANF-FG3T-11.1% composite hydrogel is 1.42 W m-1 K-1, which is attributed to the synergistic effect of the solid thermal conductivity network and the liquid convection network, resulting in a high thermal conductivity of the composite hydrogel. The high thermal conductivity of the PVA-ANF-FG3T-11.1% composite hydrogel shows great potential for flexible wearable electronics and cooling paste applications.

3.
ACS Appl Mater Interfaces ; 15(35): 41793-41805, 2023 Sep 06.
Artículo en Inglés | MEDLINE | ID: mdl-37616220

RESUMEN

Colorless polyimides (CPIs) are a key substrate material for flexible organic light-emitting diode (OLED) displays and have attracted worldwide attention. Here, in this paper, the dispersion and interfacial interaction of aromatic polyamide (PA) in CPI (synthesized from 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 2,2'-bis(trifluoromethyl)benzidine (TFMB)) were significantly improved by in situ polymerization, and colorless transparent macromolecular polyimide composites (CPI-PAx) were successfully prepared by PA and CPI. By adjusting the ratio of PA to CPI, a high-performance engineering plastic with excellent film-forming properties was obtained. Molecular simulations confirmed the uniform distribution of PA in CPI and its interaction in polymers. In CPI-PAx, the CPI was locked by the PA chain, and numerous molecular chains were mutually entangled to form a hydrogen-bond network structure. Due to the strong interaction between the chains imparted by the hydrogen bonds of the PA, they do not slide under external forces and heating. In addition, the additive PA has excellent dimensional stability, thermal, and mechanical properties, and CPI has outstanding optical properties, so the synthesized CPI-PAx combines the comprehensive properties of PA and CPI. The CPI-PAx has excellent thermal and mechanical properties, with a thermal decomposition temperature of 499 °C, a glass transition temperature of 385 °C, a coefficient of thermal expansion of 0.8 ppm K-1, a tensile strength of 50.9 MPa, and an elastic modulus of 3.9 GPa. Particularly, CPI-PAx has a 90% transmittance in the visible region. These data prove that the strategy of combining PA and CPI by in situ polymerization is an effective method to circumvent the bottleneck of CPI in the current flexible window application, and this design strategy is universal.

4.
Molecules ; 28(4)2023 Feb 18.
Artículo en Inglés | MEDLINE | ID: mdl-36838949

RESUMEN

In this paper, an effective method for preparing poly (p-phenylene terephthalamide) -co- poly (dodecanedioyl) decylamine (PA10T/1012)/graphene oxide (GO) composites by pre-dispersion and one-step in situ polymerization was proposed for the first time. During the process of polycondensation, the condensation between the terminal amino groups of PA10T/1012 chains and the oxygen-containing functional groups of GO allowed nylon to be grafted onto graphene sheets. The effects of polymer grafting on the thermal and mechanical properties of (PA10T/1012)/GO composites were studied in detail. Due to the interaction between PA10T/1012 grafted graphene sheets and its matrix, GO is well dispersed in the PA10T/1012 matrix and physically entangled with it, forming a cross-linked network structure of polymer bridged graphene, thus obtaining enhanced tensile strength, tensile modulus and impact strength. More importantly, benefiting from the cross-linked network structure, the heat distortion temperature (HDT) of the composite is greatly increased from 77.3 °C to 144.2 °C. This in situ polycondensation method opens a new avenue to prepare polycondensate graphene-based composites with high strength and high heat distortion temperatures.


Asunto(s)
Grafito , Nylons , Temperatura , Polimerizacion , Grafito/química , Calor , Polímeros/química
5.
ACS Appl Mater Interfaces ; 14(31): 36143-36156, 2022 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-35901316

RESUMEN

Two aromatic polyamides─poly(3,3'-dihydroxybenzidine terephthalamide) (DHTA) and poly(3,3'-dihydroxybenzidine isophthalamide) (DHIA)─are compared for their ability to remove salts from water. DHTA is linear and rigid whereas DHIA is nonlinear and semirigid. DHTA and DHIA were selected as they allow us to investigate the effect of polymer backbone geometry on salt exclusion in a non-crosslinked thin film membrane, independently of the backbone chemistry. Because of their differences in solution viscosity, spin coating parameters for DHTA and DHIA solutions were optimized separately to produce thin film composites (TFCs) with reproducible membrane properties. The resulting DHTA TFCs displayed salt rejections of 87.8% (NaCl), 97.0% (MgSO4), and 80.3% (CaCl2). In comparison, DHIA TFCs demonstrated poor salt rejections of 21.0% (NaCl), 29.3% (MgSO4), and 15.4% (CaCl2). Cross-sectional SEM images of DHTA and DHIA films reveal that DHTA has a stratified (layered) morphology whereas DHIA exhibits a dense, featureless morphology. Both DHTA and DHIA TFCs exhibit similar surface morphology, contact angle, surface charge, and water uptake. PEG rejection experiments indicate that the average pore size of DHTA TFCs is ∼2 nm while DHIA TFCs have an average pore size of ∼3 nm. Our findings illustrate that using a rigid, linear aromatic polyamide gives an active layer with a stratified morphology, uniplanar orientation, smaller pores, and higher salt rejection, whereas the nonlinear aromatic polyamide analogue results in an isotropic active layer with larger pores and lower salt rejection.

6.
Waste Manag ; 137: 275-282, 2022 Jan 01.
Artículo en Inglés | MEDLINE | ID: mdl-34814073

RESUMEN

Poly-p-phenylene terephthamide (PPTA) is widely applied in bulletproof products and composite materials because of its high strength, high modulus, high temperature resistance and creep resistance. The PPTA molecule with highly symmetrical and regular structure is linear structure formed by the alternating connection of benzene ring and amide bond, and the amide bonds between the molecular chains form strong hydrogen bonds. Therefore, the dissolution and depolymerization of PPTA is very challenging. In this work, an efficient catalytic system was developed for the controllable degradation of waste PPTA, and the high-value added monomers terephthalic acid (TPA) and p-phenylenediamine (PPD) were recovered. The results show that the amide bonds of PPTA can be selectively cleaved by the strong Brönsted base catalysts in alcohols, especially in the NaOH/n-butanol system. Under the optimal degradation conditions (5 wt% NaOH in n-butanol, 180 °C, 6 h), the percentage degradation of PPTA is 100%, and the yields of TPA and PPD are 92.0% and 91.5%, respectively. In addition, it is found that the wettability of n-alcohols on PPTA monofilament and the addition of a small amount of water have important influences on the degradation of PPTA. The work elucidates the degradation mechanism of PPTA, and reveals the important factors affecting the depolymerization of PPTA.


Asunto(s)
Alcoholes , Cicloparafinas , Amidas , Catálisis
7.
Membranes (Basel) ; 11(11)2021 Nov 22.
Artículo en Inglés | MEDLINE | ID: mdl-34832135

RESUMEN

Since 2000, seawater reverse osmosis method has been a dominant desalination technology against the distillation method in the global market. The large project called "Mega-SWRO" (half mega-ton per day and larger) plant in the Middle East is quite popular making full use of the combination with solar energy. Today, the price of desalinated water is affordable at as low as $0.28/m3 to $0.53/m3. Likewise, dominant commercial reverse osmosis membrane is a cross-linked fully aromatic polyamide composite membrane-spiral wound element including FT-30 (DuPont Water Solution) and UTC-80 (Toray Industries., Inc., Otsu, Shiga, Japan). The said membranes are much superior in terms of performance compared to the cellulose triacetate membranes-hollow fiber for variety of applications including seawater desalinations, brackish water desalination, wastewater reuse, ultra-pure production for semiconductor, home-use water purifier, etc. SWCC of Saudi Arabia has announced that it intends to shift from cellulose triacetate hollow fiber to spiral wound RO membranes at all of its plants. Furthermore, the state-sponsored R&D on membrane and membrane process has been put into practice in major countries, including Japan and Korea, which contributed to the progress of membrane science and membrane process, suitable for spiral-wound polyamide membranes. SWCC has announced their plans for SWRO, mainly focusing on brine mining to obtain precious materials from the brine of SWRO. New and innovative brine-mining technology has been introduced for green desalination.

8.
Polymers (Basel) ; 13(4)2021 Feb 15.
Artículo en Inglés | MEDLINE | ID: mdl-33672061

RESUMEN

Fiber reinforced thermoplastics (FRTP), reinforced with glass or carbon fibers, are used to improve the mechanical strength of injection-molded products. However, FRTP has problems such as the formation of weld lines, the deterioration of appearance due to the exposure of fibers on the molded product surface, and the deterioration of the strength of molded products due to the fiber orientation in the molded products. We have designed and fabricated an injection mold capable of melt flow control and induction heating and cooling. This mold can both heat and cool the injection mold. It can also control the melt flow direction using a movable core pin. In this study, the above-mentioned mold was used for the molding of carbon fiber reinforced semi-aromatic polyamide. As a result, we found that increasing the heating temperature of the mold and increasing melt flow control volume contribute to the prevention of the generation of a weld line and the exposure of fibers on the molded product surface, as well as to the formation of a flat surface and increased bending strength. The relationships of these results with the carbon fiber orientation in the molded products and the crystallization of semi-aromatic polyamide were also examined in this study.

9.
J Sep Sci ; 44(9): 1931-1938, 2021 May.
Artículo en Inglés | MEDLINE | ID: mdl-33533566

RESUMEN

Herein, a novel hyperbranched aromatic polyamide-coated magnetic sorbent was prepared by in situ polymerization on the surface of amino-functionalized Fe3 O4 nanoparticles. The magnetic sorbent was characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, elemental analysis, Brunauer-Emmett-Teller measurement, and X-ray photoelectron spectroscopy, etc. The new magnetic sorbent was used in the magnetic solid-phase extraction for the detection of seven benzoylurea insecticides. Under optimum conditions, low method detection limits (0.56-1.20 ng/mL), acceptable coefficient of determination (0.9967-0.9996), wide linear ranges (2.5-500.0 ng/mL), and good repeatability (intraday: 2.0-7.3%; interday: 1.9-9.2%) were achieved. The magnetic solid-phase extraction method based on the new magnetic sorbent showed good reliability in the analysis of seven benzoylurea insecticides in real water samples, as the relative recoveries were in the range from 80.1 to 116.3% with satisfactory RSDs (0.1-9.8%). By means of density functional theory and semiempirical quantum mechanical, the binding configuration and interaction energy of hyperbranched aromatic polyamide and benzoylurea insecticides were calculated. The result of theoretical calculation revealed that the adsorption of benzoylurea insecticides by hyperbranched aromatic polyamide was derived from hydrogen bonding and π-π stacking. The contribution of π-π stacking was greater than that of hydrogen bond, which was confirmed by energy decomposition analysis.

10.
Polymers (Basel) ; 13(1)2020 Dec 23.
Artículo en Inglés | MEDLINE | ID: mdl-33374700

RESUMEN

In this study, a carbon fiber-reinforced thermoplastic composite was fabricated using a new aromatic polyamide (APA) as a matrix. Non-isothermal crystallization behaviors in the cooling process of APA resin (a semi-crystalline polymer) and composite were analyzed by using a differential scanning calorimeter (DSC). To determine the optimum molding conditions, processing parameters such as the molding temperature and time were varied during compression molding of the Carbon/APA composite. The tensile and flexural properties and morphologies of the fabricated composites were analyzed. Molding at 270 °C and 50 MPa for 5 min. showed relatively good mechanical properties and morphologies; thus, this condition was selected as the optimal molding condition. In addition, to enhance the thermal conductivity of the Carbon/APA composite, a study was conducted to add hexagonal boron nitride (h-BN) as a filler. The surface of h-BN was oxidized to increase its miscibility in the resin, which resulted in better dispersity in the APA matrix. In conclusion, a Carbon/APA (h-BN) composite manufactured under optimal molding conditions with an APA resin containing surface-treated h-BN showed a thermal conductivity more than twice that of the case without h-BN.

11.
Polymers (Basel) ; 13(1)2020 Dec 27.
Artículo en Inglés | MEDLINE | ID: mdl-33375409

RESUMEN

A series of novel thermoplastic elastomers based on (poly(decamethylene terephthalamide/decamethylene isophthalamide), PA10T/10I) and poly(ethylene glycol) (PEG) were synthesized via a facile one-pot, efficient and pollution-free method. The thermal analysis demonstrates that the melting points of the resultant elastomers were in the range of 217.1-233.9 °C, and their initial decomposition temperatures were in the range of 385.3-387.5 °C. That is higher than most commercial polyamide-based thermoplastic elastomers. The tensile strength of the resultant elastomers ranges from 21.9 to 41.1 MPa. According to the high-temperature bending test results, the resultant samples still maintain considerably better mechanical properties than commercial products such as Pebax® 5533 (Arkema, Paris, France), and these novel thermoplastic elastomers could potentially be applied in high-temperature scenes. The non-isothermal crystallization kinetics of the resultant elastomers and PA10T/10I was investigated by means of Jeziorny and Mo's methods. Both of them could successfully describe the crystallization behavior of the resultant elastomers. Additionally, the activation energy of non-isothermal crystallization was calculated by the Kissinger method and the Friedman equation. The results indicate that the crystallization rates follow the order of TPAE-2000 > TPAE-1500 > PA10T/10I > TPAE-1000. From the crystallization analysis, the crystallization kinetics and activation energies are deeply affected by the molecular weight of hard segment.

12.
Polymers (Basel) ; 10(7)2018 Jul 19.
Artículo en Inglés | MEDLINE | ID: mdl-30960719

RESUMEN

This work investigated the synthesis of a novel low melting temperature polyamide 6 (PA6) copolyamide (PA6-BABT/SA) with different aliphatic/aromatic units weight content using a melt poly-condensation process. The bio-based aromatic N¹,N4-bis(4-aminobutyl) terephthalamide diamine (BABT) and long-chain aromatic polyamide salt (BABT/SA, salt of BABT, and sebacic acid), components used for the synthesis of copolyamides, were obtained from bio-based monomers. For the first time, the pertinent BABT/SA aromatic polyamide salt was isolated as a white solid and completely characterized. By varying the weight ratio of BABT/SA salt, a series of copolyamides with different molecular weights and physical properties were prepared. The aromatic BABT/SA salt disrupted crystallization of the final copolyamides and lowered the onset of melting. The Fourier transform infrared spectroscopy and X-ray diffraction results indicated a steady decrease in the degrees of crystallinity with increasing BABT/SA salt segment ratio. Furthermore, compared to neat PA6, the obtained PA6-BABT/SA copolymers possessed a similar thermal stability and high transparency, but lower glass transition temperature around human body temperature. The PA6-BABT/SA copolymers with number-average molecular weight ≥30,000 Da presented good mechanical properties, specifically showing excellent tensile strength and elongation at break up to 105.2 MPa and 218.3%, respectively.

13.
Polymers (Basel) ; 10(8)2018 Aug 02.
Artículo en Inglés | MEDLINE | ID: mdl-30960781

RESUMEN

We present basic experimental data and the theoretical background of a novel technique for fiber spinning from polymer solutions. The principal feature of the advanced process is realization of phase separation with detachment of a solvent, accompanied by the orientation of macromolecules, under the action of high extension rates. This is similar in some respects to dry spinning, though the driving force is not diffusion with subsequent evaporation of a solvent but redistribution of polymer-solvent interactions in favor of polymer-polymer and solvent-solvent ones governed by mechanical stresses. A promise of this approach has been demonstrated by experiments performed with polyacrylonitrile solutions in different solvents and solutions of the rigid-chain aromatic polyamide. We examined mechanotropic fiber spinning in model experiments with stretching jets from a drop of polymer solution in different conditions, and then demonstrated the possibility of realizing this process in the stable long-term continuous mode. During extension, phase separation happens throughout the whole section of a jet, as was confirmed by visual observation. Then a solvent diffuses on a jet surface, forming a liquid shell on the oriented fiber. Instability of this cover due to surface tension leads either to formation of separate solvent drops "seating" on the fiber or to the flow of a solvent down to the Taylor cone. The separate liquid droplets can be easily taken off a fiber. The physics underlying this process is related to the analysis of the influence of macromolecule coil-to-stretched chain transition on the intermolecular interaction.

14.
J Colloid Interface Sci ; 406: 178-85, 2013 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-23830320

RESUMEN

A novel aromatic polyamide dendrimer-TiO2 hybrid photocatalyst functionalized with spirolactam-based molecular switch (RG-TiO2) was synthesized. The materials were characterized by FT-IR and scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and UV-vis diffuse reflectance spectroscopy, in comparison with reference materials (plain TiO2). The photocatalytic activity and photostability of RG-TiO2 were investigated based on the degradation of phenol under visible light irradiation. The results showed that the RG-TiO2 hybrid photocatalyst enhanced photocatalytic efficiency of photodegradation of phenol compared with the as-prepared plain TiO2 under visible light irradiation. More significantly, when the RG-TiO2 was acidified to pH 3, the RG-TiO2 was readily transformed from spirolactam form (OFF) to the ring-opened amide form (ON). And the photocatalytic stability of ring-opened RG-TiO2 (switch off form) was much lower than that of ring-closed RG-TiO2 (switch on form). The novel fabrication method of the TiO2 photocatalyst provides a valuable way for developing highly efficient and controllable photocatalysts by molecular switch.

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