Oxydiphthalic Anhydride Research Articles

Semi-Alicyclic Thermoplastic Polyimide Matrixes Based on Hydrogenated Pyromellitic Dianhydride and Asymmetrical 3,4′-Oxydianiline with Good Thermal Stability and Improved Optical Transparency

Thermoplastic polyimide (PI) matrixes, including PI-a (cc-34ODA) and PI-b (ct-34ODA) were prepared via the hot-pressing procedures of the resins derived from the 3,4′-oxydianiline (34ODA) and two alicyclic dianhydrides of 1S,2R,4S,5R-hydrogenated pyromellitic dianhydride (ccHPMDA) and 1R,2S,4S,5R-hydrogenated pyromellitic dianhydride (ctHPMDA), respectively. The resins exhibited thermoplastic features with good formability at higher temperatures. The afforded semi-alicyclic PI sheets exhibited enhanced properties in comparison to commercially available, wholly aromatic thermoplastic PIs, such as PI-ref1, which are derived from 3,3′,4,4′-oxydiphthalic anhydride (ODPA) and 4,4′-oxydianiline (44ODA), as well as PI-ref2, which is based on pyromellitic dianhydride (PMDA) and 4,4′-bis(3-aminophenoxy)biphenyl (mBAPB). In addition, the developed PI sheets exhibited high heat deflection temperatures (HDT) of 267.4 °C for PI-a and 268.6 °C for PI-b. There values were significantly higher when compared with those of PI-ref1 (Ratem® YS20, HDT: 239.0 °C), PI-ref2 (Aurum® PL450C, HDT: 238.0 °C), PI-ref3 (Ultem® 1000, HDT: 206.0 °C), PI-ref4 (Therplim® TO65, HDT: 180.0 °C), and PI-ref5 based on phthalic anhydride-terminated fluorinated PIs (HDT: 215.0 °C). In terms of mechanical properties, the current PI sheets showed superior flexural properties among the polymers with the flexural strength of 189.0 ± 11.7 MPa (PI-a) and 200.5 ± 4.2 MPa (PI-b), respectively. In addition, the PI sheets exhibited comparable compression properties, inferior impact strength, and tensile properties compared with the referenced PI counterparts. Basically, the PI-b sheet showed better comprehensive properties than those of the stereoisomeric PI-a analog.

Synthesis and properties of new polyimide foams from foaming compositions with flexible segments of aliphatic diamine

AbstractNew foaming prepolymer compositions based on 4,4′‐oxydiphthalic anhydride, 4,4′‐diaminodiphenyl ether, 1,6‐hexamethylenediamine (HMDA), and a surfactant were synthesized. Polyimide (PI) foams containing from 0 to 40 mol% HMDA were prepared. The possibility of controlling the pore sizes in a foam material by selecting different fractions (250–400 μm) of particles of the powdered foam composition for heat treatment was shown. Scanning electron microscopy studies of morphology of the synthesized PI foams (PIFs) showed that all foams exhibited open cellular structures with pore diameters ranging from 50 to 500 μm. The influence of the components of the foaming composition (surfactant and aliphatic diamine) on the structure, thermal, and mechanical properties of the resulting PIFs was traced. The samples of PIFs containing 20% and 30% HMDA were elastic (the corresponding stress–strain curves were almost linear up to the 30% deformation) and able to restore their shape after removing the load. The resulting foams exhibited high thermal stability (the onset of weight loss was observed in the 470–500°C range). It was revealed that the synthesized PIF compositions were incombustible in an open flame. Due to their high heat resistance and nonflammability, the obtained PIFs can be used for thermal insulation applications in the aerospace, transport, construction, and microelectronics industries.Highlights New, lightweight, flexible, and nonflammable PIFs have been synthesized. The HMDA additive imparts elasticity to PIFs. The introduction of a surfactant (KT‐6) makes the PIF homogeneous.

Excellent thermal conductivity and electrical insulation in polyimide/graphene oxide/carbon nanotubes composites

AbstractPolymer composites with heat resistance, good thermal conductivity, and insulation properties can meet the special needs of electronics and electrical appliances. In this work, graphene oxide (GO) and carbon nanotubes (CNTs) are coated by polydopamine (PDA). 4,4′‐diaminodiphenyl ether (ODA), pyromellitic dianhydride (PMDA), and 4,4′‐oxydiphthalic anhydride (ODPA) in‐situ polymerize to prepare poly(amide acid) (PAA) containing thermally conductive yet insulating fillers (PDA@GO, PDA@CNTs). As the concentration of fillers in PI composites increases, the thermal conductivity rises, but the insulation property decreases. Keeping the filler content constant and varying the ratio of PDA@GO and PDA@CNTs, the thermal conductivity increases and then decreases. When PDA@GO and PDA@CNTs have a mass ratio of 10:1, the significant synergistic effect affects the thermal conductivity. The PI/PG10C1–25 sample has a thermal conductivity of 1.46 W/(m·K), which is 6.9 times greater than the pure PI. Additionally, the volume resistivity, dielectric permittivity, and dielectric loss (100 kHz) of PI/PG10C1–25 are 2.8 × 1013 Ω cm, 5.4 and 0.28, respectively. The heat resistance of PI composites is almost the same as that of pure PI. Given these outstanding attributes, the developed PI composites offer vast applications in many fields.Highlights Synergistic PDA@GO and PDA@CNTs (10:1) optimize thermal conductivity. PI/PG10C1–25 achieves 6.9 times higher thermal conductivity than pure PI. Volume resistivity of PI/PG10C1–25 reaches 2.8 × 1013 Ω·cm. Dielectric permittivity of PI/PG10C1–25 reaches 5.4 at 100 kHz. Developed PI composites maintain excellent heat resistance.

Molecular design of free volume structure in thermally rearranged polybenzoxazole membranes for gas separation studied by positron annihilation

AbstractIn this work, 2,2‐bis(3‐amino‐4‐hydroxyphenyl) hexafluoropropane (APAF) was used as the fixed diamine monomer, and 4,4′‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), 3,3′,4,4′‐biphenyltetracarboxylic diandhydride (BPDA) and pyromellitic dianhydride (PMDA) were selected as four different dianhydride monomers, respectively, to prepare the thermally rearranged polybenzoxazole (TR‐PBO) gas separation membranes with different structures via a thermal rearrangement reaction at 450°C. The microstructure of TR‐PBO membranes was investigated using X‐ray diffraction and positron annihilation spectroscopy. All the TR‐PBO membranes exhibit bimodal free volume structure, containing ultramicropores (<0.7 nm) and micropores (<2 nm) with size of 3.6–4.6 and 7.6–8.4 Å, respectively. As the steric hindrance of the bridging groups in the dianhydride monomers increases, the radius and number of pores in the membranes increases, leading to an increase in fractional free volume (FFV). The pure gas permeation test shows a positive correlation between gas permeability and FFV in the TR‐PBO membranes, indicating that an increase in FFV is favorable for the diffusion of gas molecules. Particularly, the ultramicropores play a decisive role on the gas selectivity. All the TR‐PBO membranes exhibit excellent gas permeaselectivity. Among them, the H2/CH4 separation performance of APAF‐6FDA and APAF‐ODPA membranes approaches the 2008 Robeson upper bound, which is due to the high number of both micropores and ultramicropores. Our results demonstrate that the free volume structure of polymer membranes can be designed by selecting monomers with different structures and utilizing thermal rearrangement reactions, allowing for the preparation of gas separation membranes with high permeability and selectivity.

Polyimides with ultra-low coefficient of thermal expansion derived from diamine containing bisbenzimidazole and bisamide

To provide polyimide (PI) with high heat resistance and ultra-low coefficient of thermal expansion (CTE) for use in flexible display substrates, a novel diamine with bisbenzimidazole and bisamide groups, namely N,N'-(1H,1'H-[5,5'-bibenzo[d]imidazole]-2,2'-diyl)bis(4-aminobenzamide) (BZBA), was designed and successfully synthesized. Several poly(benzimidazole-amide-imide) (PBIAI) films were prepared by thermal imidization with 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), and 4,4'-(hexafluoroisopropylindene)-diphthalic anhydride (6FDA), respectively. Among them, BZBA-BPDA has a high glass transition temperatures ( Tg = 345 °C) while achieving an extremely low coefficients of thermal expansion (CTE = 1.9 ppm K−1), meeting the processing requirements of polymer flexible substrates in OLED devices. The effects of different dianhydrides on the performance of PBIAIs were compared, providing a meaningful reference for further adjusting the PI molecular structure to meet specific requirements for industrial polymer films.

Constructing high-toughness polyimide binder with robust polarity and ion-conductive mechanisms ensuring long-term operational stability of silicon-based anodes

Silicon-based materials have demonstrated remarkable potential in high-energy–density batteries owing to their high theoretical capacity. However, the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode. Herein, a functionalized high-toughness polyimide (PDMI) is synthesized by copolymerizing the 4,4′-Oxydiphthalic anhydride (ODPA) with 4,4′-oxydianiline (ODA), 2,3-diaminobenzoic acid (DABA), and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane (DMS). The combination of rigid benzene rings and flexible oxygen groups (-O-) in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness. The plentiful polar carboxyl (–COOH) groups establish robust bonding strength. Rapid ionic transport is achieved by incorporating the flexible siloxane segment (Si-O-Si), which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport (9.8 × 10−10 cm2 s−1 vs. 16 × 10−10 cm2 s−1). As expected, the SiOx@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85% over 500 cycles at 1.3 A g−1. The well-designed functionalized polyimide also significantly enhances the electrochemical properties of Si nanoparticles electrode. Meanwhile, the assembled SiOx@PDMI-1.5/NCM811 full cell delivers a high retention of 80% after 100 cycles. The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity electrodes for high-energy–density batteries.

Monomer Dependence of Colorless and Transparent Polyimide Films: Thermomechanical Properties, Optical Transparency, and Solubility.

Six poly(amic acid)s (PAAs) were synthesized by reacting bis(3-aminophenyl) sulfone with various dianhydride monomers such as pyromellitic dianhydride, 4,4'-biphthalic anhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, 4,4'-oxidiphthalic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride. These PAAs were then converted to polyimide (PI) films by thermal imidization at various temperatures. To obtain colorless and transparent PI (CPI), the dianhydride monomer used in this study had an overall bent structure, a structure containing a strong electron-withdrawing -CF3 substituent or an alicyclic ring. In addition, some monomers contained ether or ketone functional groups in their bent structures. The thermomechanical properties, optical transparency, and solubility of CPI films with six different dianhydride monomer structures were investigated, and the correlation between the monomer structure and CPI film properties was clarified. Overall, CPI with an aromatic main chain structure or a linear structure had excellent thermal and mechanical properties. In contrast, CPI with a bent structure containing functional groups or substituents in the main chain exhibited excellent optical transparency and solubility.

Heat-resistant carbon fiber composite materials based on fusible oligoimide

In this work, oligoimide powder binders of the IDA type based on 4,4’-’oxydiphthalic anhydride and bis-(4-acetamido)diphenyl oxide with different molecular weights were obtained. CFRPs were obtained by electrostatic spraying of a powdered oligoimide binder onto a carbon fabric, followed by high-temperature calendering and hot pressing of prepregs. The thermal and mechanical characteristics of the obtained carbon composites are determined.

Effects of various types of organo-mica on the physical properties of polyimide nanocomposites

Poly(amic acid) (PAA) was synthesized using dianhydride 4,4’-oxydiphthalic anhydride and diamine 3,3'-dihydroxybenzidine, and polyimide (PI) hybrid films were synthesized by dispersing organo-mica in PAA through a solution intercalation method. Hexadimethrine-mica (HM-Mica), 1,2-dimethylhexadecylimidazolium-mica (MI-Mica), and didodecyldiphenylammonium-mica (DP-Mica), which were obtained via the organic modification of pristine mica, were used as the organo-micas for the PI hybrid films. The organo-mica content was varied from 0.5 to 3.0 wt% with respect to the PI matrix. The thermomechanical properties, morphology, and optical transparency of the resultant PI hybrid films were measured and compared. Dispersion of even small amounts of organo-mica effectively improved the physical properties of the PI hybrids, and maximum enhancements in physical properties were observed at a specific critical content. Electron microscopy of the hybrid films revealed that the organo-mica uniformly dispersed throughout the polymer matrix at the nanoscale level when added at low contents but aggregated in the matrix when added at levels above the critical content. Structural changes in the organo-mica closely influenced the changes in the physical properties of the hybrid films. All PI hybrid films with various organo-mica contents showed similar optical properties, but that prepared with MI-Mica demonstrated the best thermomechanical properties. All synthesized PI hybrid films were transparent regardless of the type and content of organo-mica used.

Ultrafast Hole Transfer in Graphitic Carbon Nitride Imide Enabling Efficient H2O2 Photoproduction.

Solar-driven photocatalysis is a promising approach for renewable energy application. H2O2 photocatalysis by metal-free graphitic carbon nitride has been gaining attention. Compared with traditional thermal catalysis, metal-free graphitic carbon nitride photocatalysis could lower material cost and achieve greener production of H2O2. Also, to better guide photocatalyst design, a fundamental understanding of the reaction mechanism is needed. Here, we develop a series of model cost-effective metal-free H2O2 photocatalysts made from graphitic carbon nitride (melem) and common imide groups. With 4,4'-oxydiphthalic anhydride (ODPA)-modified g-C3N4, a H2O2 yield rate of 10781 μmol/h·g·L could be achieved. Transient absorption and ex situ Fourier transform infrared (FTIR) measurements revealed an ultrafast charge transfer from the melem core to water with ∼3 ps to form unique N-OH intermediates. The electron withdrawing ability of the anhydride group plays a role in governing the rate of electron transfer, ensuring efficient charge separation. Our strategy represents a new way to achieve a low material cost, simple synthesizing strategy, good environment impact, and high H2O2 production for renewable energy application.

Preparation and characterization of low CTE thermoplastic copolyimide resins based on the structural design of block sequence

In order to solve the challenge of balancing the thermoplastic processing properties and thermal dimensional stability of polyimide (PI) resin, in this research, 3,3′,4,4′-biphenyl tetracarboxylic diandhydride (BPDA) and 2,2′-bis(trifluoromethyl)benzidine (TFMB) were used as rigid components, 4,4′-oxydiphthalic anhydride (ODPA) and 4,4′-diaminodiphenyl sulfone (DDS) as flexible components. A series of random copolyimide resins was prepared by adjusting the molar ratio of rigid and flexible monomers. Determining the molar ratio which could balance the thermoplastic processing properties and thermal dimensional stability, block copolyimide resins with different rigid and flexible block lengths were then prepared in this ratio. The research showed that the molar ratio of monomers and the sequence structure of molecular chains had a strong influence on the performance of PI resins. When the content or block length of rigid component increased, the coefficient of thermal expansion (CTE) decreased but the glass transition temperatures (Tg) and melt viscosity increased. The PI-B343 resin had a CTE value of 40.63 ppm/K and the lowest melt viscosity reached 675 Pa·s, achieved the simultaneous regulation of the thermoplastic processing properties and thermal dimensional stability for PI resin.

Investigating the structure–sensitivity relationship of photosensitive polyimide formulated by using a photobase generator

AbstractPhotosensitive polyimides (PSPIs) have been widely used in the buffer coating layer and insulation layer due to their excellent thermal and mechanical stability. In this work, a series of negative‐type PSPIs based on poly(amic acid) (PAA) and a photobase generator (PBG) have been developed. Two diamines of 4,4′‐oxydianiline (ODA), 3,3′‐diaminodiphenyl sulfone (SDA), and four dianhydrides of pyromellitic dianhydride (PMDA), 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐oxydiphthalic anhydride (ODPA) and cyclobutene‐1,2,3,4‐tetracarboxylic dianhydride (CBDA) are copolymerized to PAA through polyaddition, and the PAA is further thermally imidized to polyimide (PI). Through scrutinizing the structure–sensitivity relationship of these PIs, we find that the rigidity and transparency of the PAA/PI backbone play an important role in the sensitivity and contrast of PSPI. Accordingly, PSPI (SDA‐ODPA), possessing high optical transparency and a low rigidity represented by the low glass transition point, is capable of providing good photosensitivity of 30 mJ/cm2, a high contrast of 2.46, and an excellent pattern resolution of 4 μm after optimizing the prebaking (100°C for 5 min), exposure dose (380 mJ/cm2), post‐exposure baking (130°C for 7 min), and development parameters. This work provides the concept of structural design for negative‐type PSPI in the microelectronic application.

Studies on the Application of Polyimidobenzimidazole Based Nanofiber Material as the Separation Membrane of Lithium-Ion Battery.

Aromatic polyimide has good mechanical properties and high-temperature resistance. Based on this, benzimidazole is introduced into the main chain, and its intermolecular (internal) hydrogen bond can increase mechanical and thermal properties and electrolyte wettability. Aromatic dianhydride 4,4'-oxydiphthalic anhydride (ODPA) and benzimidazole-containing diamine 6,6'-bis [2-(4-aminophenyl)benzimidazole] (BAPBI) were synthesized by means of a two-step method. Imidazole polyimide (BI-PI) was used to make a nanofiber membrane separator (NFMS) by electrospinning process, using its high porosity and continuous pore characteristics to reduce the ion diffusion resistance of the NFMS, enhancing the rapid charge and discharge performance. BI-PI has good thermal properties, with a Td5% of 527 °C and a dynamic mechanical analysis Tg of 395 °C. The tensile strength of the NFMS increased from 10.92MPa to 51.15MPa after being hot-pressed. BI-PI has good miscibility with LIB electrolyte, the porosity of the film is 73%, and the electrolyte absorption rate reaches 1454%. That explains the higher ion conductivity (2.02 mS cm-1) of NFMS than commercial one (0.105 mS cm-1). When applied to LIB, it is found that it has high cyclic stability and excellent rate performance at high current density (2 C). BI-PI (120 Ω) has a lower charge transfer resistance than the commercial separator Celgard H1612 (143 Ω).

A simple strategy to simultaneously improve the lifetime and activity of classical iridium complex for photocatalytic water‐splitting

AbstractHerein, we design and synthesize a series of oligomers [Ir(ppy)2(dabpy)‐ODPA]n (D1‐n) by copolymerization of [Ir(ppy)2(dabpy)][PF6] (D2) with 4,4′‐Oxydiphthalic anhydride (ODPA), to resolve the problem of simultaneous improvement of stability and activity of classical iridium complex for photocatalytic water‐splitting. Fourier‐transform infrared spectroscopy, X‐ray photoelectron spectroscopy, solid‐state nuclear magnetic resonance, and gel permeation chromatography results indicate that the degree of polymerization (n) of D1‐n could be tuned by the synthesis method. The best photocatalytic performance is reached by D1‐n with n at of 2 and/or 3 (D1‐2/3), which exhibits a photocatalytic lifetime up to 676 h and a photocatalytic hydrogen evolution of 162055.1 μmol·g‐1. Compared with classical iridium complex D2, the photocatalytic lifetime of D1‐2/3 is about 38 times longer and the photocatalytic activity is 1.3 times higher. Further increase of n leads to a decrease in both photocatalytic lifetime and activity. According to the spectroscopic characterizations, photoelectrochemical experiments, and density functional theory calculation, the significantly enhanced photocatalytic performance of D1‐2/3 originates from the oligomeric structure. The oligomer chain of D1‐2/3 with suitable length acts as a large steric hindrance to reduce the undesired photoinduced decomposition and prolong its lifetime. The possible coupling of adjacent Ir complexes in D1‐2/3 lowers the energy gap and increases the utilization of visible light, which overcomes the adverse effect of large steric hindrance and finally improve the activity. This work first provides a simple strategy for constructing oligomeric Ir photosensitizers to simultaneously achieve long lifetime and high activity, it will lay the foundation for the design of highly efficient photosensitizers in the future.

Colorless and transparent poly(amide imide) nanocomposites containing organically modified hectorite.

Polyamic acid (PAA) was synthesized using the diamine monomer N,N'-[2,2'-bis(trifluoromethyl)-4,4'-biphenylene]bis(4-aminobenzamide) and dianhydride monomer 4,4'-oxydiphthalic anhydride. Colorless and transparent poly(amide imide) (CPAI) hybrid films were prepared via multi-step thermal imidization of PAA in which various contents of nano-filler were dispersed. The CPAI hybrid films were prepared by dispersing organoclay STN, which was obtained by organically modifying hectorite, in CPAI by solution intercalation with various contents ranging from 1 to 7 wt%. The thermomechanical properties, morphologies, and optical transparencies of the obtained CPAI hybrid films were investigated based on the dispersed STN content, and the results were compared. Some of the clay in the CPAI hybrid film were agglomerated, which was observed using a transmission electron microscope; however, most clays were well-dispersed, with a nano-size of less than 10 nm. The best thermomechanical properties of the CPAI hybrid film were exhibited with an STN content of 3 wt%, but these properties decreased above the critical content. The coefficients of thermal expansion of all the hybrid films were below 20 ppm per °C regardless of the amount of STN, and the yellow index was 1-2 even when the STN content increased to 7 wt%.

Electrospun Benzimidazole-Based Polyimide Membrane for Supercapacitor Applications.

A benzimidazole-containing diamine monomer was prepared via a simple one-step synthesis process. A two-step procedure involving polycondensation in the presence of aromatic dianhydrides (4,4′-oxydiphthalic anhydride, ODPA) followed by thermal imidization was then performed to prepare a benzimidazole-based polyimide (BI-PI). BI-PI membranes were fabricated using an electrospinning technique and were hot pressed for 30 min at 200 °C under a pressure of 50 kgf /cm2. Finally, the hot-pressed membranes were assembled into supercapacitors, utilizing high-porosity-activated water chestnut shell biochar as the active material. The TGA results showed that the BI-PI polymer produced in the two-step synthesis process had a high thermal stability (Td5% = 527 °C). Moreover, the hot-press process reduced the pore size in the BI-PI membrane and improved the pore-size uniformity. The hot-press procedure additionally improved the mechanical properties of the BI-PI membrane, resulting in a high tensile modulus of 783 MPa and a tensile strength of 34.8 MPa. The cyclic voltammetry test results showed that the membrane had a specific capacitance of 121 F/g and a capacitance retention of 77%. By contrast, a commercial cellulose separator showed a specific capacitance value of 107 F/g and a capacitance retention of 49% under the same scanning conditions. Finally, the membrane showed both a small equivalent series resistance (Rs) and a small interfacial resistance (Rct). Overall, the results showed that the BI-PI membrane has significant potential as a separator for high-performance supercapacitor applications.

Methylethynyl-Terminated Polyimide Nanofibrous Membranes: High-Temperature-Resistant Adhesives with Low-Temperature Processability.

As an alternative to traditional riveting and welding materials, high-temperature-resistant adhesives, with their unique advantages, have been widely used in aviation, aerospace, and other fields. Among them, polyimide (PI) adhesives have been one of the most studied species both from basic and practical application aspects. However, in the main applications of solvent-type PI adhesives, pinholes or bubbles often exist in the cured PI adhesive layers due to the solvent volatilization and dehydration reaction, which directly affect the adhesive performance. To address this issue, electrospun PI nanofibrous membranes (NFMs) were employed as solvent-free or solvent-less adhesives for stainless steel in the current work. To enhance the adhesion of PI adhesives to the metal substrates, phenolphthalein groups and flexible ether bonds were introduced into the main chain of PIs via the monomers of 4,4′-oxydiphthalic anhydride (ODPA) and 3,3-bis[4-(4-aminophenoxy)phenyl] phthalide (BAPPT). At the same time, the methylethynyl group was used as the end-capping component, and the crosslinking reaction of the alkynyl group at high temperature further increased the adhesive strength of the PI adhesives. Three kinds of methylethynyl-terminated PI (METI) NFMs with the set molecular weights of 5000, 10,000, and 20,000 g/mol were first prepared via the one-step high-temperature polycondensation procedure. Then, the PI NFMs were fabricated via the standard electrospinning procedure from the soluble METI solutions. The afforded METI NFMs showed excellent melt-flowing behaviors at high temperature. Incorporation of the methylethynyl end-capping achieved a crosslinking reaction at 280−310 °C for the NFMs, which was about 70 °C lower than those of the phenylacetylene end-capping counterparts. Using the METI NFMs as adhesive, stainless steel adherends were successfully bonded, and the single-lap shear strength (LSS) was higher than 20.0 MPa at both room temperature (25 °C) and high temperature (200 °C).

New polyimides containing methyl benzamidobenzoate or dimethyl benzamidoisophthalate as bulky pendant groups. Effects on solubility, thermal and gas transport properties

AbstractThis work reports the synthesis of six new polyimides obtained by the reaction of two novel diamine monomers: methyl 4‐(3,5‐diaminobenzamido)benzoate and dimethyl 5‐(3,5‐diaminobenzamido)isophthalate, bearing one or two methyl ester groups in their phenyl rings, respectively, with three known dianhydrides, 4,4′‐(hexafluoroisopropylidene) diphatalic anhydride (6FDA), 4,4′‐(dimethylsilanediyl) dipthalic anhydride (SiDA) and 4,4′‐oxydiphthalic anhydride (ODPA). The polyimides were synthesized using the “two‐step” method, which first involves forming a poly(amic acid) precursor that is subsequently cyclodehydrated to form the imide linkage. The yields were higher than 95% in all cases, and the structural characterization was performed by spectroscopic techniques like FT‐IR, 1H, 13C, and 29Si NMR. In addition, the effect on the solubility in common organic solvents and thermal and gas transport properties of these polyimides were studied as a function of the nature of the respective side group and the dianhydride used.

Clarifying the effect of chemical structure on high-temperature resistance of polyimides based on DFT and ReaxFF based molecular dynamic simulation

In this work, the pyrolysis route and high-temperature resistance of 3,3′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA)/p-phenylenediamine (p-PDA), BPDA/m-phenylenediamine (m-PDA), BPDA/3,5-diaminobenzoic acid (DABA), BPDA/4,4′-oxydianiline (ODA), pyromellitic dianhydride (PMDA)/ODA, and 4,4′-oxydiphthalic anhydride (ODPA)/ODA were studied by molecular simulation and thermogravimetric analysis (TGA). Simulation based on density functional theory (DFT) was used for isothermal pyrolysis simulation of single-chain block copolymer models; molecular dynamics (MD) based on reaction force field (ReaxFF) was used for isothermal pyrolysis simulation of condensed state models. Two novel and facile methods, named as fragment counting method and total substances counting method, respectively, were proposed to evaluate the high-temperature resistance and explore the pyrolysis mechanisms of PIs. The results show that the BPDA/p-PDA PI presents the best thermostability. Compared with p-PDA, introducing m-PDA and DABA promotes the cleavages of C–N bonds and benzene rings to impair the high-temperature stability of PIs molecular chains. In addition, carboxyl groups in DABA lead to the release of large amounts of CO2 during pyrolysis process. The cleavage of ether bonds in ODA and ODPA is observed at the early stage of pyrolysis, therefore leading to significant decrease of high-temperature resistance of PIs. PMDA slightly reduces the high-temperature resistance of PIs compared with BPDA when the diamine unit is ODA. Besides, 2 kinds of pyrolysis mechanisms are revealed by analyzing the proportion of volatiles in the by-products. In DABA-containing PIs, the pyrolysis process is dominated by the generation of volatiles and molecular chains breakage, and presents two-stage weight loss, which is considered as the first pyrolysis mechanism. The pyrolysis process of DABA-free PIs is dominated by molecular chains cleavage, and displays only one-stage weight loss, which is considered as the second mechanism. The above simulation results are in good agreement with the experimental results from TGA, proving the reliability of the simulation. Mayer bond order (MBO) analysis of the target PI models was performed, and it is found that varying the chemical structure will lead to significant changes of bond strength, which is suggested to be one of the important reasons affecting the high-temperature stability and pyrolysis process of PIs. This work is believed to be of great help to the molecular design of high-temperature resistance PIs.

Enhancement of atomic oxygen resistance for heat-sealable isomeric co-polyimide films by combining ether linkage with diphenylphosphine oxide

Heat-sealable isomeric co-polyimide (CPI) films with enhanced atomic oxygen (AO) resistance and mechanical strength were synthesized from 2,3,3′,4′-oxydiphthalic anhydride (aODPA), 4,4′-oxydianiline (ODA), and 2,5-bis [(4-aminophenoxy)phenyl]diphenylphosphine oxide (BADPO). We investigated how the molecular structure and diamine ratio affected the thermal properties, solubility, mechanical properties, AO resistance and heat-sealability. The diphenylphosphine oxide (DPO) side group decreased the CPI film mechanical strength and its higher ODA reactivity increased the molecular weight. At 10 mol% ODA in the aODPA-BADPO system, the CPI film exhibited increased tensile strength with no detriment to the AO resistance. Meanwhile, the CPI films demonstrated good heat-sealability indicated by a completely merged interface after heat sealing.