Synthesis Of Polyimides Research Articles

Polyimide synthesis and characterizations: DFT-assisted computational studies on structural units

Polyimide synthesis and characterizations: DFT-assisted computational studies on structural units

Electrospun Membranes of Hydrophobic Polyimide and NH2‐UiO‐66 Nanocomposite for Desalination

Hydrophobic nanofiber composite membranes comprising polyimide and metal–organic frameworks are developed for desalination via direct contact membrane distillation (DCMD). Our study demonstrates the synthesis of hydrophobic polyimides with trifluoromethyl groups, along with superhydrophobic UiO‐66 (hMOF) prepared by phenylsilane modification on the metal‐oxo nodes. These components are then combined to create nanofiber membranes with improved hydrophobicity, ensuring long‐term stability while preserving a high water flux. Integration of hMOF into the polymer matrix further increases membrane hydrophobic properties and provides additional pathways for vapor transport during MD. The resulting nanofiber composite membranes containing 20 wt% of hMOFs (PI‐1‐hMOF‐20) were able to desalinate hypersaline feed solution of up to 17 wt% NaCl solution, conditions that are beyond the capability of reverse osmosis systems. These membranes demonstrated a water flux of 68.1 kg m−2 h−1 with a rejection rate of 99.98% for a simulated seawater solution of 3.5 wt% NaCl at 70 °C, while maintaining consistent desalination performance for 250 h.

Synthesis and Characterization of Polyimides with Rigid Folded Fragments

The macromolecular chain of conventional polyimide (PI) is a predominant linear extension, which is anticipated to uphold robust interchain interactions essential for preserving overall mechanical and thermal performance. This study is dedicated to the design and synthesis for the novel PIs containing folded chains, with a particular emphasis on modifying the chain conformational behavior with respect to the structure of the aggregation state and the corresponding gas separation properties. First, two unidirectional diamine monomers, dibenzo [c, g] phenanthrene-9,12-diamine (NPDA) and anthracene-1,8-diamine (ADA), were meticulously synthesized through a sequence of chemical reactions, including Witting olefination and photocyclization. These monomers possess distinctive spatial characteristics: NPDA adopts a helical conformation, while ADA maintains a planar structure. Subsequently, the corresponding folded chain-containing PIs, denoted as NPI and API, were successfully achieved by copolymerizing one of the unidirectional monomers with the 6FDA-TPDA system. API and NPI generally exhibit a propensity for enhanced molecular chain stacking, while retaining their good solubility and processability. Drawing from both experimental data and simulation results, it was ascertained that the inclusion of these two monomers produces a rearrangement of pore sizes with a decrease in large-size micropores and an increase in the percentage of ultra-micropores. Moreover, the PI membranes with the folded fragments have a much better CO2 plasticization resistance.

Regularities of Single-Step Synthesis of Adamantane-Containing Polyimides in Sulfolane

Regularities of Single-Step Synthesis of Adamantane-Containing Polyimides in Sulfolane

One-pot aqueous-phase synthesis of polyimides from typical monomers

One-pot aqueous-phase synthesis of polyimides (PIs) offers great economic and environmental benefits and improves the hydrolytic stability of the precursor (polyamic acid) obviously. However, this method is only suitable for the polymerization of very limited dianhydride and diamine monomers up to now. In this study, the most commonly used dianhydrides and diamines for the preparation of commercially available PI products were selected for one-pot aqueous-phase synthesis of various polyamic acid salts (PAAS). The effects of the structure of monomers, the reaction temperature and the adding process of the organic base on the polymerization reaction were explored by rotational rheology, nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy. The polymerization products obtained via the aqueous-phase route show high molecular weight when the reaction conditions have been optimized. Various PI films prepared by the thermal imidization of corresponding PAAS demonstrate good optical transparency, excellent thermal stability, and outstanding mechanical and electrical properties. This work proposes the reaction mechanism of PAAS via one-pot aqueous-phase route and utilizes this novel polymerization strategy to synthesize high-molecular-weight PIs from typical aromatic dianhydride and diamine monomers.

Synthesis of Photosensitive Polyimides Incorporating Polydimethylsiloxane Segments and Studies on the Properties of their UV-Cured Films

Synthesis of Photosensitive Polyimides Incorporating Polydimethylsiloxane Segments and Studies on the Properties of their UV-Cured Films

Crystal Structure, Supramolecular Organization, Hirshfeld Analysis, Interaction Energy, and Spectroscopy of Two Tris(4-aminophenyl)amine-Based Derivatives

The use of tris(4-aminophenyl)amine (TAPA) as central to the synthesis of both polyimines and polyimides and covalent organic frameworks and inorganic cages, among others, has grown in the last few years. The resulting materials exhibit high performance in their area of application. In this contribution, the crystal structures of two TAPA derivatives, triethyl (nitrilotris(benzene-4,1-diyl))tricarbamate (1) and triethyl 2,2′,2″-((nitrilotris(benzene-4,1-diyl))tris(azanediyl))tris(2-oxoacetate) (2), are described. The molecular and supramolecular structures of both compounds were compared between them and with analogous compounds. The analyses of their vibrational and 13C-CPMAS NMR spectroscopies, as well as their thermal stability, were included and corelated with the crystal structure. Hirshfeld surface analysis on the crystal structures of both TAPA derivatives revealed the stabilization of the crystal network via the amide N—H∙∙∙O interactions of dispersive nature in the carbamate, whereas dispersive carbonyl–carbonyl interactions also played a competitive role in the supramolecular arrangement of the oxamate. Interaction energy DFT calculations performed at the B3LYP/6-31G(d,p) level allowed us to estimate the energy contributions and nature of several interactions in terms of the stability of both crystal lattices.

Synthesis of Co3O4-modified sulfur-doped polyimide for photocatalytic reduction of 4-nitrophenol via ion-exchange technique

Synthesis of Co3O4-modified sulfur-doped polyimide for photocatalytic reduction of 4-nitrophenol via ion-exchange technique

Synthesis of High-Performance Colorless Polyimides with Asymmetric Diamine: Application in Flexible Electronic Devices.

Colorless polyimides (CPIs) are widely used as high-performance materials in flexible electronic devices. From a molecular design standpoint, the industry continues to encounter challenges in developing CPIs with desired attributes, including exceptional optical transparency, excellent thermal stability, and enhanced mechanical strength. This study presents and validates a method for controlling 2-substituents, with a specific emphasis on examining how these substituents affect the thermal, mechanical, optical, and dielectric characteristics of CPIs. The presence of two CF3 groups on the same side of the diamine structure ensured the transmittance of the film. The charge transfer effect and the molecular distance are dynamically regulated by changing the 2-substituent (-OCH3/-CH3/H/F). The polyimide exhibited a well-maintained equilibrium between transparency and thermal stability, with a T500nm value ranging from 86.2 to 89.6% in the visible region, and a glass transition temperature (Tg) ranging from 358.6 to 376.0 °C. Additionally, the 6FDA-2-MTFMB compound, when combined with methyl, excels as a protective layer and base material, exhibiting excellent performance in various aspects. It has been verified as an appropriate option for flexible photodetectors and wearable piezoresistive sensors. In summary, this systematic investigation will provide a comprehensive and demonstrative methodology for developing CPIs that are capable of adapting to flexible electronic devices.

Design, synthesis, and characterization of intrinsic black polyimide with complete absorption of visible light and low coefficient of thermal expansion

Black polyimides (BPIs) show increasing demand in the microelectronics and optoelectronics fields. However, the existing BPIs have drawbacks of poor masking ability, dimensional stability, thermal and electrical properties. 3,6-Bis(thiophen-2-yl)diketopyrrolopyrroles (TDPP) is a typical dye that possesses a high molar extinction coefficient. In the work, a new diamine (DPPTOMePDA) bearing TDPP connected with methoxyl-substituted benzene rings was synthesized. Based on such diamine and pyromellitic dianhydride (PMDA), a high-performance intrinsic BPI (DPPTOMePPI) was obtained. The resulting DPPTOMePPI exhibited a red-shifted and broadened absorption spectrum, thus achieving complete absorption of visible light and highly black color. Its cut-off wavelength (λcut) was up to 734 nm, and the Commission International de l’Eclairage (CIE)-Lab coordinate L* decreased to 0.53. Furthermore, DPPTOMePPI exhibited excellent thermal and electrical performances with a low coefficient of thermal expansion (CTE). Density functional theory calculation was executed to analyze the underlying electron transitions of DPPTOMePPI. The results showed that the strong light absorption of DPPTOMePPI was primarily ascribed to the electronic transition of HOMO to LUMO+1 that occurred in the chromophores units. The flexible copper clad laminates (FCCLs) derived from DPPTOMePPI film showed high peel strength and resistance to solder heat. The work offers a theoretical guide for the construction of intrinsic black PI possessing complete visible absorption and low CTE.

Synthesis, characterization and film preparation of 6FDA-based polyimides with polar groups arranged for thermal crosslinking

Abstract Thermal crosslinking of polyimides is a relevant methodology to increase their chemical resistance. This reaction is induced by heating after polymerization. Although this reaction is considered a viable route to modify polyimides, there is controversy over the specific temperature for the reaction. To contribute to the knowledge of crosslinked structures, we performed a differential scanning calorimetric (DSC) and solubility test studies on a series of polyimides with different molar ratios of carboxylic acid groups. With 3,5-diaminobenzoic acid (DABA) as a source of carboxylic acid groups, the copolyimides were synthesized from 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 4,4ʹ-hexafluoropropylidenebis(p-phenylenoxy)dianiline (6FPA) to form blocks of 6FDA:6FPA (n) and 6FDA:DABA (m) from m = 0–100 %. Flat films were prepared at 50 ± 3 µm with polyimides. In the thermogram of the flat films, a heat absorption zone associated with the decarboxylation reaction was identified with an endothermic minimum at 260 °C, which was assigned to the crosslinking temperature. Furthermore, heating time was varied for 3–36 h to determine the insolubility of the thermally crosslinked polyimide; from 24 h of heating the polyimide were insoluble. The polyimides were thoroughly characterized by ATR-FTIR, 1H NMR, TGA, SEM, the fractional free volume (FFV) was determined by the Bondi’s group contribution method and solubility to different organic solvents. The FFV of crosslinked polyimides increases relative to pristine polyimides by 2 % for those with higher DABA content and 40 % for those with lower DABA content. Finally, also the glass transition temperature increases in the crosslinked polyimides relative to the pristine ones from 280 °C for the lowest DABA content to 402 °C for the highest DABA content, demonstrating the increase in the thermal resistance of the structure.

Synthesis and Characterization of Negative-Tone Photosensitive Polyimides with Low Coefficient of Thermal Expansion for Packaging Applications.

Negative-tone photosensitive polyimides (PSPIs) with a low coefficient of thermal expansion (CTE) were prepared by dissolving polyimide precursor-poly(amide ester) (PAE) resins, photoinitiators, photocrosslinkers and other additives in organic solvents. Using triamine as a monomer and dianhydride and diamine as polycondensates, tri-branched structure PAE resins with different molecular weights named PAE-1~5 were prepared. A series of corresponding PSPI films named PSPI-1~5 were prepared from PAE-1~5 resins with the same formulation, respectively. The PSPI-1~5 films prepared from resins of this structure have excellent mechanical, thermal and electrical properties after being thermally cured at 350 °C/2 h in nitrogen. The PSPI-1~5 films' coating solution also show good photolithographic performance and are able to obtain photolithographic patterns with a resolution of about 10 μm after homogenization, exposure and development. Among the PSPI-1~5 films, PSPI-2 has the most excellent lithographic properties with a weight average molecular weight (Mw) of 2.9 × 104 g/mol, a CTE of 41 ppk/°C, a glass transition temperature (Tg) of 343 °C and a 5% weight loss temperature (Td5) of 520 °C, making it suitable for industrial scale-up. The mechanical properties of elongation at breakage of 42.4%, tensile moduli of 3.4 GPa and tensile strength of 153.7 MPa were also measured.

Synthesis and properties of novel colorless polyimide containing indene and amide groups

AbstractTwo novel diamines 1‐(4‐aminophenyl)‐1,3,3‐trimethyl‐2,3‐dihydro‐1H‐indene‐5‐amine and 4‐amino‐N‐(4‐(5‐(4‐aminobenzamide)‐1,3,3‐trimethyl‐2,3‐dihydro‐1H‐inden‐1‐yl) phenyl) benzamide containing indene and amide groups were successfully designed and synthesized, and a series of colorless polyimides (CPIs) derived from the two diamines with 1,2,4,5‐cyclohexanetetracarboxylic dianhydride in various ratios were copolymerized. The introduction of aliphatic ring structures was conducive to the improvement of optical properties, while the incorporation of amide groups improved thermal and mechanical properties. These CPI films exhibited excellent optical properties (T400 > 80%), high heat resistance (Tg > 300 °C) and mechanical properties with the synergistic action of the two groups. Furthermore, the effect of the content of amide groups on the intermolecular interaction of CPIs was systematically analyzed. This study provides a fancy method for the development of heat‐resistant colorless materials for optical applications.

Synthesis and characterization of polyamides and polyimides based on diamines featuring imidazole and carbazole pendant groups: analysis of optical, thermal, and antibacterial properties

Synthesis and characterization of polyamides and polyimides based on diamines featuring imidazole and carbazole pendant groups: analysis of optical, thermal, and antibacterial properties

Synthesis and Electrophoretic Deposition of Polyimide with Methacrylic Groups on the Side Chain

Synthesis and Electrophoretic Deposition of Polyimide with Methacrylic Groups on the Side Chain

Development of New Polyimide/Spirulina Hybrid Materials: Preparation and Characterization

This study presents the synthesis and characterization of polyimide (PI-2) films incorporated with spirulina powder for potential biomedical applications. The synthesis of PI-2 was achieved through a two-step polycondensation reaction using N-methyl-2-pyrrolidone (NMP) as the solvent. The incorporation of spirulina was systematically varied to investigate its effects on the structural and surface properties of the hybrid materials. Scanning electron microscopy revealed a tightly bound interface between spirulina and the PI-2 matrix, indicating effective dispersion and strong interfacial adhesion. Profilometry and Raman spectroscopy confirmed the homogeneous integration of spirulina within the polymer matrix, with resulting variations in surface roughness and chemistry. Contact angle measurements demonstrated altered wettability characteristics, with increased hydrophilicity observed with spirulina incorporation. Furthermore, blood component interaction studies indicated the variations in adhesion behavior observed for red blood cells, platelets, and plasma proteins. Water uptake studies revealed enhanced absorption capacity in PI-2 films loaded with spirulina, highlighting their potential suitability for applications requiring controlled hydration. Overall, this comprehensive characterization elucidates the potential of PI-2/spirulina hybrid materials for diverse biomedical applications, offering tunable properties that can be tailored to specific requirements.

POLYIMIDE FILMS IMPLANTED BY MANGANESE IONS

The optical and strength properties of Kapton polyimide films implanted with manganese ions with an energy of 40 keV and a dose of 5·1016 – 1·1017 cm–2 at a current density in the ion beam of 4 μA/cm2 have been studied. It has been experimentally established that during the process of ion implantation, modification of a thin nearsurface layer of polyimide occurs not only on the implanted side, but also on the reverse side of the film. Radiationstimulated modification of the back surface of the polyimide film leads to the formation of a surface layer up to 5 μm thick with increased microhardness. This may be due to the restructuring of metastable defects formed during the film manufacturing process and the simultaneous relaxation of elastic stresses in the surface layer. During the implantation process, a decrease in the intensity of absorption bands with maxima at ~ 2870 and ~ 2750 nm is observed, due to the evaporation of residual water under high vacuum conditions and reactions of residual solvent molecules, as well as radiation-induced processes on by-products of polyimide synthesis.

ELECTRON IRRADIATED PI2610 POLYIMIDE FILMS ON MONOCRYSTALLINE SILICON

The optical and strength properties of electron-irradiated films of a polyimide composition (polyimide PI2610) deposited on the surface of single-crystalline silicon wafers of the KDB-10 grade by centrifugation were studied. Irradiation with electrons with an energy of 5 MeV was carried out on a linear accelerator U-003 in the dose range 1·1014 – 2·1015 cm–2. It has been experimentally established that at an irradiation dose of Ф = 1∙1014 cm–2, relaxation of elastic stress fields in the polyimide film is observed, which is expressed in modification of the shape of bands with maxima at 1349 and 1700 cm–1, caused by vibrations of the C–N–Cst bond and the C=O double bond imide ring. Polyimide PI-2610 films on silicon are quite stable when irradiated with electrons. A noticeable transformation of the ATR spectrum at a dose of 2∙1015 cm–2 was observed only in the region of stretching vibrations of C–H and O–H bonds, which is due to radiation-induced processes on by-products of polyimide synthesis and residual solvents. No noticeable decrease in the intensity of absorption bands caused by vibrations of the skeleton of the aromatic ring, imide ring, single and double C–C and C–O bonds, and imide C=O bonds was observed.

Synthesis and characterization of high Tg and colorless polyamide-imide films derived from amide-containing diamines with different trifluoromethyl substitution

Four new diamines (3TFDABA, 2TFDABA, 22TFDABA and TFAPTA) were successfully synthesized to investigate the effect of different trifluoromethyl (CF3) substitution position on poly(amide-imide)s (PAIs) properties. High-performance PAIs were prepared from high-temperature polycondensation of these diamines with 6FDA dianhydride. All the PAI films exhibited good heat resistance with glass-transition temperatures (Tgs) of 311–392 °C, good 5% weight loss temperatures (Td5%s) of 480–510 °C in nitrogen, and excellent optical transparency with T450 ranging from 52% to 84%. According to the monomer structural design, a high heat resistant and colorless poly(amide-imide) film (PAI-2-6FDA), with excellent optical properties (T450 of 82%), outstanding thermal properties (Td5% of 499 °C and Tg of 392 °C), and good mechanical properties (tensile strength of 123 MPa, tensile modulus of 4.4 GPa) was achieved. A comprehensive structure-to-property relationship study revealed that the CF3 in ortho-position of the amino group effectively inhibited the rotation between imide ring and benzene, thus improved the heat resistance of the film. Moreover, it could also weaken the generation of charge transfer complexes through strong electron-withdrawing ability, which is beneficial for the synthesis of colorless polyimides.

Thermal hazard assessment of polyimide synthesis at different viscosities using calorimetry

Thermal hazard assessment of polyimide synthesis at different viscosities using calorimetry