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New Membrane-Forming Aromatic Co-Poly(amide-imide)s: Influence of the Chemical Structure on the Morphological, Thermal and Transport Properties.

ABSTRACT: Polymer film membranes are used to solve specific separation problems that dictate structural requirements. Structural and morphological parameters of film membranes based on glassy polyheteroarylenes can be controlled in the process of preparation from solutions that opens up prospects for obtaining structured membranes required for targeted separation. In the case of aromatic poly(amide-imide)s, the possibility of controlling film formation and structure virtually has not been studied. In the present work, a series of homologous co-poly(amide-imide)s differing in the number of repeating units with carboxyl-substituted aromatic fragments was synthesized by polycondensation. Comparative analysis of the processes of formation of membranes with different morphologies based on these polymers under equal conditions was performed. New information was obtained about the influence of the amounts of carboxyl groups and the residual solvent on structural properties of asymmetric membranes. The influence of these factors on transport properties of dense membranes under pervaporation conditions was studied. It was demonstrated that in the case of carboxyl-containing poly(amide-imide)s, the domains formed during film preparation had a significant effect on membrane properties.

SUBMITTER: Kononova SV

PROVIDER: S-EPMC8781751 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Poly(amide-imide) materials for transparent and flexible displays.

Project description:The key component currently missing for the next generation of transparent and flexible displays is a high-performance polymer material that is flexible, while showing optical and thermal properties of glass. It must be transparent to visible light and show a low coefficient of thermal expansion (CTE). While specialty plastics such as aromatic polyimides are promising, reducing their CTE and improving transparency simultaneously proved challenging, with increasing coloration the main problem to be resolved. We report a new poly(amide-imide) material that is flexible and displays glass-like behavior with a CTE value of 4 parts per million/°C. This novel polymer was successfully used as a substrate to fabricate transparent and flexible indium-gallium-zinc oxide thin-film transistors.

| S-EPMC6203221 | biostudies-literature

A Highly Hydrophilic and Biodegradable Novel Poly(amide-imide) for Biomedical Applications.

Project description:A novel biodegradable poly(amide-imide) (PAI) with good hydrophilicity was synthesized by incorporation of l-glycine into the polymer chain. For comparison purposes, a pure PAI containing no l-glycine was also synthesized with a three-step method. In this study, we evaluated the novel PAI's thermal stability, hydrophilicity, solubility, biodegradability and ability to support bone marrow mesenchymal stem cell (BMSC) adhesion and growth by comparing with the pure PAI. The hydrophilic tests demonstrated that the novel PAI has possible hydrophilicity at a 38° water contact angle on the molecule surface and is about two times more hydrophilic than the pure PAI. Due to an extra unit of l-glycine in the novel PAI, the average degradation rate was about 2.4 times greater than that of the pure PAI. The preliminary biocompatibility studies revealed that all the PAIs are cell compatible, but the pure PAI exhibited much lower cell adhesion than the l-glycine-incorporated novel PAI. The hydrophilic surface of the novel PAI was more suitable for cell adhesion, suggesting that the surface hydrophilicity plays an important role in enhancing cell adhesion and growth.

| S-EPMC6432413 | biostudies-literature

Bio-based Aromatic Copolyesters: Influence of Chemical Microstructures on Thermal and Crystalline Properties.

Project description:Aromatic copolyesters, derived from bio-based nipagin and eugenol, were synthesized with renewable 1,6-hexandiol as the spacer. Number-average, weight-average molecular weights (Mn, Mw), and polydispersity (D) values were determined by size exclusion chromatography (SEC). Chemical structures were confirmed by 1H NMR and 13C NMR spectroscopies. Chemical microstructure analysis suggested that the nipagin and eugenol-derived units were inserted into polymer chains in an arbitrary manner. Due to the short chain of 1,6-hexanediol, the splitting of magnetically different methylene carbons, adjacent to the alcohol-oxygens, proved to be more sensitive towards sequence distributions, at the dyed level, than those from 1,10-decanediol. Thermal gravimetric analysis (TGA) demonstrated that these polyester materials have excellent thermal stability (> 360 °C), regardless of the content of eugenol-derived composition incorporated. Differential scanning calorimetric (DSC) and wide-angle X-ray diffraction (WXRD) experiments revealed the semicrystalline nature for this kind of copolyesters. The crystallinities gradually decreased with the increase of eugenol-derived composition. Thermal and crystalline properties were well discussed from the microscopic perspective. The point of this work lies in establishing guidance for future design and modification of high-performance polymer materials from the microscopic perspective.

| S-EPMC7240576 | biostudies-literature

Amide-forming chemical ligation via O-acyl hydroxamic acids.

Project description:The facile rearrangement of "S-acyl isopeptides" to native peptide bonds via S,N-acyl shift is central to the success of native chemical ligation, the widely used approach for protein total synthesis. Proximity-driven amide bond formation via acyl transfer reactions in other contexts has proven generally less effective. Here, we show that under neutral aqueous conditions, "O-acyl isopeptides" derived from hydroxy-asparagine [aspartic acid-?-hydroxamic acid; Asp(?-HA)] rearrange to form native peptide bonds via an O,N-acyl shift. This process constitutes a rare example of an O,N-acyl shift that proceeds rapidly across a medium-size ring (t1/2 ? 15 min), and takes place in water with minimal interference from hydrolysis. In contrast to serine/threonine or tyrosine, which form O-acyl isopeptides only by the use of highly activated acyl donors and appropriate protecting groups in organic solvent, Asp(?-HA) is sufficiently reactive to form O-acyl isopeptides by treatment with an unprotected peptide-?thioester, at low mM concentration, in water. These findings were applied to an acyl transfer-based chemical ligation strategy, in which an unprotected N-terminal Asp(?-HA)-peptide and peptide-?thioester react under aqueous conditions to give a ligation product ultimately linked by a native peptide bond.

| S-EPMC5899448 | biostudies-other

Influence of the Preparation Method and Photo-Oxidation Treatment on the Thermal and Gas Transport Properties of Dense Films Based on a Poly(ether-block-amide) Copolymer.

Project description:Dense films based on the hydrophobic Pebax®2533 were prepared by using solution casting in different solvents as well as compression molding and subjected to photo⁻aging under ultraviolet (UV) irradiation. The influence of the preparation method, including the casting solvents, as well as the UV irradiation time selected to treat the samples, were evaluated in terms of permeation rates of pure gases (CO₂, N₂, O₂, CH₄, He, and H₂). The transport data were correlated with the microstructure and surface properties by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS), as well as water contact angle measurements. The obtained results showed that a controlled photo-oxidation process reduces the hydrophobicity of the Pebax®2533 films, increasing their permeability without compromising their integrity.

| S-EPMC6119977 | biostudies-literature

Dynamic Polyamide Networks via Amide-Imide Exchange.

Project description:The diamide-imide equilibrium was successfully exploited for the synthesis of dynamic covalent polymer networks in which a dissociative bond exchange mechanism leads to high processibility at temperatures above ≈110 °C. Dynamic covalent networks bridge the gap between thermosets and thermoplastic polymers. At the operating temperature, when the network is fixed, dynamic covalent networks are elastic solids, while at high temperatures, chemical exchange reactions turn the network into a processible viscoelastic material. Upon heating a dissociative network, the viscosity may also decrease due to a shift of the chemical equilibrium; in such materials, the balance between processibility and excessive flow is important. In this study, a network is prepared that upon heating to above ≈110 °C dissociates to a significant extent due to a shift in the amide-imide equilibrium of a bisimide, pyromellitic diimide, in combination with poly(tetrahydrofuran) diamines. At room temperature, the resulting materials are elastic rubbers with a tensile modulus of 2-10 MPa, and they become predominantly viscous above a temperature of approximately 110 °C, which is dependent on the stoichiometry of the components. The diamide-imide equilibrium was studied in model reactions with NMR, and variable temperature infrared (IR) spectroscopy was used to investigate the temperature dependence of the equilibrium in the network. The temperature-dependent mechanical properties of the networks were found to be fully reversible, and the material could be reprocessed several times without loss of properties such as modulus or strain at break. The high processibility of these networks at elevated temperatures creates opportunities in additive manufacturing applications such as selective laser sintering.

| S-EPMC8552437 | biostudies-literature

Influence of Mixed Imide Composition and Thermal Annealing on Ionic Liquid Uptake and Conductivity of Polyimide-Poly(ethylene glycol) Segmented Block Copolymer Membranes.

Project description:Understanding the impact of different bridging groups in the two-step polymerization of poly(ethylene glycol) (PEG)-incorporated polyimide (PI) materials is significant. It is known that the proton exchange membranes (PEMs) used in industry today can experience performance degradation under rising temperature conditions. Many efforts have been devoted to overcoming this problem by improving the physical and mechanical properties that extend the hygrothermal life of a PEM. This work examines the effect of oxygenated and fluorinated bridging anhydrides in the production of PI-PEG PEMs. It is shown that the dianhydride identity and the amount incorporated in the synthesis influences the properties of the segmented block copolymer (SBC) membranes, such as increased ionic liquid uptake (ILU), enhanced conductivity and higher Young's modulus favoring stiffness comparable to Nafion 115, an industrial standard. Investigations on the ionic conductivity of PI-PEG membranes were carried out to determine how thermal annealing would affect the material's performance as an ion-exchange membrane. By applying a thermal annealing process at 60 °C for one hour, the conductivities of synthesized segmented block copolymer membranes values were increased. The effect of thermal annealing on the mechanical properties was also shown for the undoped SBC via measuring the change in the Young's modulus. These higher ILU abilities and mechanical behavior changes are thought to arise from the interaction between PEG molecules and ethylammonium nitrate (EAN) ionic liquid (IL). In addition, higher interconnected routes provide a better ion-transfer environment within the membrane. It was found that the conductivity was increased by a factor of ten for undoped and a factor of two to seven for IL-doped membranes after thermal annealing.

| S-EPMC8705581 | biostudies-literature

Azobenzene Functionalized "T-Type" Poly(Amide Imide)s vs. Guest-Host Systems-A Comparative Study of Structure-Property Relations.

Project description:This paper describes the synthesis and characterization of new "T-type" azo poly(amide imide)s as well as guest-host systems based on the "T-type" matrices. The matrices possessed pyridine rings in a main-chain and azobenzene moieties located either between the amide or imide groups. The non-covalent polymers contained the molecularly dispersed 4-phenylazophenol or 4-[(4-methyl phenyl)diazinyl]phenol chromophores that are capable of forming intermolecular hydrogen bonds with the pyridine rings. The FTIR spectroscopy and the measurements of the thermal, optical and photoinduced optical birefringence were employed for the determination of the influence of H-bonds and the specific elements of polymer architecture on physicochemical properties. Moreover, the obtained results were compared to those described in our previous works to formulate structure-property relations that may be considered general for the class of "T-type" azo poly(amide imide)s.

| S-EPMC7215900 | biostudies-literature

Structure and thermal transitions in a biomedically relevant liquid crystalline poly(ester amide).

Project description:There is still a need to develop bioresorbable polymers with high strength and high modulus for load-bearing biomedical applications. Here we investigate the liquid crystalline structural features of poly(desaminotyrosyl-tyrosine dodecyl dodecanedioate), poly(DTD DD), a new bioresorbable poly(ester amide) that is currently studied in vivo as a slow-degrading implantable biomaterial for load bearing applications. Thermally induced structural changes in poly(DTD DD) were studied using simultaneously differential scanning calorimetry (DSC) and X-ray scattering. The hexatic SmB organization of the polymer chains that exists at room temperature becomes progressively disordered upon heating, changing into a SmF phase and then into a smectic C phase at 60°C before turning into a free flowing melt at 130°C. X-ray scattering data and thermal analysis indicate the presence of a 2D ordered structure in the polymer melt. A structural model with an interesting 3-fold symmetry in the packing of the side chains around the rigid aromatic main chain, and the packing of these chains into fibrils is proposed. The liquid crystalline behavior of poly(DTD DD) makes it possible to melt process it at low temperatures without thermal degradation. This is a noteworthy advantage for the use of poly(DTD DD) as a high strength, readily processable, yet biodegradable polymer.

| S-EPMC6827981 | biostudies-literature

Enhancement of Thermal Diffusivity in Phase-Separated Bismaleimide/Poly(ether imide) Composite Films Containing Needle-Shaped ZnO Particles.

Project description:Phase-separated polymer blend composite films exhibiting high thermal diffusivity were prepared by blending a soluble polyimide (BPADA-MPD) and a bismaleimide (BMI) with needle-shaped zinc oxide (n-ZnO) particles followed by high-temperature curing at 250 °C. Images recorded with a field-emission scanning electron microscope (FE-SEM) equipped with wavelength-dispersive spectroscopy (WDS) demonstrated that the spontaneously separated phases in the composite films were aligned along the out-of-plane direction, and the n-ZnO particles were selectively incorporated into the BMI phase. The out-of-plane thermal diffusivity of the composite films was significantly higher than those of the previously reported composite films at lower filler contents. Based on wide-angle X-ray diffraction (WAXD) patterns and image analysis, the enhanced thermal diffusivity was attributed to the confinement of the anisotropically shaped particles and their nearly isotropic orientation in one phase of the composite films.

| S-EPMC6432426 | biostudies-literature

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