Hexafluoropropane Dianhydride Research Articles

Soluble Fluorinated Cardo Copolyimide as an Effective Additive to Photopolymerizable Compositions Based on Di(meth)acrylates: Application for Highly Thermostable Primary Protective Coating of Silica Optical Fiber.

The development of photocurable compositions is in high demand for the manufacture of functional materials for electronics, optics, medicine, energy, etc. The properties of the final photo-cured material are primarily determined by the initial mixture, which needs to be tuned for each application. In this study we propose to use simple systems based on di(meth)acrylate, polyimide and photoinitiator for the preparation of new photo-curable compositions. It was established that a fluorinated cardo copolyimide (FCPI) based on 2,2-bis-(3,4-dicarboxydiphenyl)hexafluoropropane dianhydride, 9,9-bis-(4-aminophenyl)fluorene and 2,2-bis-(4-aminophenyl)hexafluoropropane (1.00:0.75:0.25 mol) has excellent solubility in di(met)acrylates. This made it possible to prepare solutions of FCPI in such monomers, to study the effect of FCPI on the kinetics of their photopolymerization in situ and the properties of the resulting polymers. According to the obtained data, the solutions of FCPI (23 wt.%) in 1,4-butanediol diacrylate (BDDA) and FCPI (15 wt.%) in tetraethylene glycol diacrylate were tested for the formation of the primary protective coatings of the silica optical fibers. It was found that the new coating of poly(BDDA-FCPI23%) can withstand prolonged annealing at 200 °C (72 h), which is comparable or superior to the known most thermally stable photo-curable coatings. The proposed approach can be applied to obtain other functional materials.

Temperature-Controlled Chain Dynamics in Polyimide Doped with CoCl2 Probed Using Dynamic Mechanical Analysis.

Cobalt(II) chloride (CoCl2) being in the vicinity of polyimide chains entails modifications in terms of the molecular dynamics, which are mainly governed by the possible presence of amic acid residual groups, by the transition-metal-type characteristics of cobalt and by the CoCl2 content. Polyimide was synthesized using poly(amic acid) according to the reaction of 2,2'-bis(3,4-dicarboxylphenyl)hexafluoropropane dianhydride (6FDA) with 3,3'-dimethyl-4,4'-diaminodiphenylmethane (MMDA) in N,N-dimethylacetamide. CoCl2 was added before the thermal imidization of the poly(amic acid). An experimental approach was designed to establish the interaction between the polyimide and CoCl2 and whether the interaction depends on the quantity of the salt. Evidence for the existence of residual amic acid groups was obtained using second derivative Fourier Transform Infrared Spectroscopy (FTIR) and with the help of 2D correlation spectroscopy (2D-COS). Moreover, FTIR, along with X-ray photoelectron spectroscopy (XPS), revealed the interaction between the polymer and CoCl2, primarily in the form of Co(II)-N coordinated bonds. Nevertheless, the coordination of cobalt with suitable atoms from the amic acid groups is not precluded. The results of dynamic mechanical analysis (DMA) featured a specific relaxation assigned to the presence of CoCl2 in the polymeric film and demonstrated that its (non)reinforcing effect depends on its content in the polyimide.

Study on Chemical Graft Structure Modification and Mechanical Properties of Photocured Polyimide.

The great challenge facing additive manufacturing is that the available high-performance 3D printing materials can hardly keep up with the rapid development of new additive manufacturing technology. Then, the commercial resins available in the market have some problems, such as poor thermal stability, insufficient light-curing degree, and large shrinkage after curing, which need to be solved urgently. This study reports a photocurable polyimide ink for digital light processing (DLP) 3D printing to prepare controllable 3D structures with high thermal stability, low shrinkage, and excellent comprehensive properties. In this study, pyromellitic dianhydride and diaminodiphenyl ether, the Kapton polyimide with the highest performance synthesized so far, were selected as raw materials, and 2,2′-bis(3,4-dicarboxylic acid) hexafluoropropane dianhydride containing fluorine was introduced to modify the branched-chain structure. The polyimide was prepared by one-step imidization, and then the graft with photocurable double bonds and certain functions was grafted by reaction of glycidyl methacrylate with phenolic hydroxyl groups. In this work, the solubility of the synthesized oligomer polyimide in organic solvents was greatly increased by combining three methods, thereby allowing the formation of ink for photocuring 3D printing, and the ink can be stacked to form low-shrinkage polyimide with complex controllable shape. Polyimide printed by DLP can produce complex structures with good mechanical character and thermal stability and small shrinkage. Therefore, the polyimide prepared in this study is considered to be a resin of great commercial possibility. In addition, due to its properties, it has important development potential in some fields with high demand for thermal stability, such as high-temperature cooling valves, aerospace, and other fields.

Gas separation performance of solid-state in-situ thermally crosslinked 6FDA-based polyimides

2,2-Bis(3,4-dicarboxyphenyl)-hexafluoropropane dianhydride (6FDA)-derived polyimides containing polar functional groups have been extensively studied for membrane-based gas separations and used as precursors for various solid-state thermal modifications such as thermal crosslinking of carboxyl-groups or thermal rearrangement of hydroxyl groups to form polybenzoxazoles. In this work, we studied four 6FDA-derived polyimides without polar functional groups to investigate in-situ thermal crosslinking involving partial decomposition of the hexafluoroisopropylidene (–C(CF3)2–) mainchain group. A thorough examination of the 6FDA-based polyimides via thermal gravimetric analysis coupled with mass spectroscopy (TGA-MS) and energy dispersive X-ray spectroscopy (EDX) under isothermal treatment at 450 °C for up to 3 h revealed that thermal treatment triggered continuous evolution of fluorine from (–C(CF3)2–) groups. The 6FDA-based polyimides were insoluble after thermal treatment for only 30 min and maintained good mechanical strength with favorable changes in gas separation properties. For example, after 3 h isothermal heat treatment, the CO2 permeability of crosslinked 6FDA-pPDA noticeably increased threefold from 39 to 115 barrer coupled with only a small drop in CO2/CH4 selectivity from 54 to 46. The crosslinked polyimides demonstrated excellent plasticization resistance when tested under high-pressure binary CO2/CH4 mixed-gas conditions.

Synthesis and characteristics of HAB‐6FDA thermally rearranged polyimide nanocomposite membranes

AbstractThe thermal rearrangement of polyimides of ortho‐positioned functional group membranes improves the gas permselectivity properties of the polyimide precursor. For this experiment, HAB‐6FDA polyimide was synthesized from 3,3 dihydroxy‐4,4‐diamino‐biphenyl (HAB) and 2,2‐bis‐(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) by chemical imidization. A sample was modified from a pure polymer to silica nanoparticle composition. Furthermore, a modification was carried out by thermal rearrangement reaction at temperatures of 350, 400, and 450°C. The thermal property of these membrane films was characterized by differential scanning calorimetry (DSC), FTIR, opacity experiment, and free volume analysis. Permeability decreases with an increase in the kinetic diameter of gasses, which is normal behavior for glassy polymers. The composition of silica nanoparticles slightly changes the permeability in the polyimide. The combined effect of silica nanoparticles and thermal rearrangement of the HAB‐6FDA membrane has shown an excellent performance. The thermal rearrangement with nanocomposite shows a significant impact on a larger effect on permeation for lighter gases, that is, H2, CO2, and O2, compared with N2 and CH4. Particularly for H2/CH4 gas pair, it lies over Robeson's 2008 upper bound limit, which fits the composition in the novel class for the gas separation membranes.

Preparation and Characterization of Electrospun Fluoro-Containing Poly(imide-benzoxazole) Nano-Fibrous Membranes with Low Dielectric Constants and High Thermal Stability.

The rapid development of advanced high-frequency mobile communication techniques has advanced urgent requirements for polymer materials with high-temperature resistance and good dielectric properties, including low dielectric constants (low-Dk) and low dielectric dissipation factors (low-Df). The relatively poor dielectric properties of common polymer candidates, such as standard polyimides (PIs) greatly limited their application in high-frequency areas. In the current work, benzoxazole units were successfully incorporated into the molecular structures of the fluoro-containing PIs to afford the poly(imide-benzoxazole) (PIBO) nano-fibrous membranes (NFMs) via electrospinning fabrication. First, the PI NFMs were prepared by the electrospinning procedure from organo-soluble PI resins derived from 2,2′-bis(3,4-dicarboxy-phenyl)hexafluoropropane dianhydride (6FDA) and aromatic diamines containing ortho-hydroxy-substituted benzamide units, including 2,2-bis[3-(4-aminobenzamide)-4-hydroxylphenyl]hexafluoropropane (p6FAHP) and 2,2-bis[3-(3-aminobenzamide)-4-hydroxyphenyl]hexafluoropropane (m6FAHP). Then, the PI NFMs were thermally dehydrated at 350 °C in nitrogen to afford the PIBO NFMs. The average fiber diameters (dav) for the PIBO NFMs were 1225 nm for PIBO-1 derived from PI-1 (6FDA-p6FAHP) precursor and 816 nm for PIBO-2 derived from PI-2 (6FDA-m6FAHP). The derived PIBO NFMs showed good thermal stability with the glass transition temperatures (Tgs) over 310 °C and the 5% weight loss temperatures (T5%) higher than 500 °C in nitrogen. The PIBO NFMs showed low dielectric features with the Dk value of 1.64 for PIBO-1 and 1.82 for PIBO-2 at the frequency of 1 MHz, respectively. The Df values were in the range of 0.010~0.018 for the PIBO NFMs.

Free volume manipulation of a 6FDA-HAB polyimide using a solid-state protection/deprotection strategy

Tert-butoxycarbonyl (t-BOC) is a thermally labile moiety that can be used to protect hydroxyl groups on polymers. In this study, t-BOC was appended onto a polyimide consisting of 2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 3,3′-dihydroxy-4,4′-diamino-biphenyl (HAB), after which the polymer was formed into self-standing films. Solid-state thermal treatments were performed to systematically remove t-BOC moieties to alter the physical packing structure and concomitant gas transport properties of the polymer. Despite performing deprotection reactions well below the glass transition temperature of 6FDA-HAB (~300 °C), this free volume manipulation (FVM) approach produced only subtle differences in polymer density, fractional free volume, average free volume element size, and gas transport properties relative to the unprotected polymer. While these findings suggest that thermally removing covalently bound functional groups from polymer films can be used to manipulate free volume and gas transport performance for glassy polymers, more robust polymer systems than linear polyimides are required to preserve the nascent free volume architecture generated from this approach.

Preparation and properties of propargyl ether-terminated poly(imide siloxane)s and their composites

The novel propargyl ether-terminated oligo(imide siloxane)s (PTISs) based on 2,2’-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), aminopropyl-terminated polydimethylsiloxane (APPS), 4,4’-diaminodiphenylmethane (MDA) and p-aminophenyl propargyl ether (APPE) were synthesized. The chemical structures of PTISs were characterized by proton nuclear magnetic resonance (1H NMR) and Fourier transform infrared spectroscopy (FTIR). The PTISs exhibited excellent solubility in organic solvent and had broad processing window. The T300 carbon fabric was used to reinforce the PTIS matrices and prepare the composites (T300CF/PTISs). The thermal stability of the cured PTISs was analyzed by thermogravimetric analysis (TGA). The dynamic thermal mechanical properties of the composites were measured by dynamic thermomechanical analysis (DMA). The results show that the temperature at 5% weight loss (Td5) and residual yield at 800°C (Yr800°C) of the cured PTISs in N2 increase with incorporation of the aromatic diamine, whereas the Yr800°C of the cured PTISs in air decreases with introduction of the aromatic diamine. The elasticity of the composite increases with incorporation of the aromatic diamine, and the peak temperature of loss factor for the composites are higher than 300°C. The flexural strength, tensile strength and interlaminar layer shear strength (ILSS) of the T300CF/PTIS composite display the values of 439 MPa, 427 MPa and 32 MPa at room temperature, respectively. The retention of the flexural strength and ILSS for the T300CF/PTIS composite are above 80% at 250°C.

Effects on Carbon Molecular Sieve Membrane Properties for a Precursor Polyimide with Simultaneous Flatness and Contortion in the Repeat Unit.

Carbon molecular sieve (CMS)-based membrane separation is a promising solution for hydrogen separation due to its great advantages on perm-selectivity, thermal stability, and chemical stability. To prepare high-performance CMS membranes, the molecular structure of polymer precursors and their arrangements should be primarily considered. In this work, a benzimidazole-based 6FDA (2,2'-bis(3,4'-dicarboxyphenyl) hexafluoropropane dianhydride)-type polyimide (PABZ-6FDA-PI) is chosen as precursor to prepare the CMS membrane. Effects of chain flatness and contortion in the polyimide precursor on gas-separation performance of CMS membranes were studied in detail by gas adsorption and permeation experiment. The H2 permeability of CMS is up to 9500 Barrer and ideal selectivity of gas pairs of H2 /CH4 and H2 /CO2 is up to 3800 and 13, respectively. The comprehensive performance of hydrogen separation including H2 /CO2 , H2 /N2 , and H2 /CH4 gas pairs is located well above previously reported upper bounds for polymers.

Competitive sorption in CO2/CH4 separations: the case of HAB-6FDA polyimide and its TR derivative and a general analysis of its impact on the selectivity of glassy polymers at multicomponent conditions

CO2 and CH4 mixed-gas solubility was measured in 3,3′-dihydroxy-4,4′-diamino-biphenyl (HAB) 2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) polyimide and in its thermally rearranged (TR) derivative, TR450. Due to competitive sorption effects, the solubility of both species in mixed-gas conditions is lower than the corresponding pure-gas solubility at the same fugacity. CH4 sorption is significantly affected by the presence of the second gas, while CO2 behavior is hardly altered. Therefore, the multicomponent solubility-selectivity is higher than the ideal value calculated from pure-gas sorption data, and this has a positive impact on CO2/CH4 separation properties. The multicomponent solubility data were modelled with the Non-Equilibrium Lattice Fluid (NELF) model, using only pure component parameters and binary interaction parameters obtained from pure-gas sorption data available in the literature, with no parameters determined from the mixed-gas sorption data. Although it is easier to use, the multicomponent Dual Mode Sorption (DMS) model yielded less accurate predictions of mixed-gas sorption. Mixed-gas sorption experiments and modelling, coupled with mixed-gas permeation data, enabled a better fundamental understanding of the separation properties of these materials. Unlike the case of pure-gas experiments, where diffusivity contributes more to the overall ideal selectivity, competitive sorption is the main effect governing the permselectivity of these membrane materials at multicomponent conditions. A systematic comparison with literature data on mixed-gas CO2/CH4 sorption and permeability revealed these to be generalized trends, obeyed by materials of very different chemical constitution. This finding can inform on the criteria that make polymers performing better in multicomponent scenarios, with potential impact on the design and synthesis strategies of new materials.

Gas separation properties of aromatic polyimides with bulky groups. Comparison of experimental and simulated results

A series of new diamine monomers, with systematic variations in their chemical structure, by introducing various substituents onto the polymer backbone, have been made to react with two commercial dianhydrides: a very rigid one, pyromellitic dianhydride, (PMDA) and a more flexible one, 2,2′-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), to obtain a series of polyimide membranes with high fractional free volume (FFV), and their gas separation properties have been studied. In order to gain insight into the relationship between structure and gas separation properties of the polymers, a computer simulation of the polymers has been carried out, by a combination of molecular mechanics and molecular dynamics, to study the effect of the polymeric structure on the permeability and selectivity of the membranes. Moreover, the effect of the probe size on the accessible free volume, which cannot be experimentally determined, has been simulated and related with experimental gas separation parameters as permeability and selectivity. The use of FFV (that corresponds to a probe of zero-radius) cannot predict the behavior of several polymers, which have similar FFV values but different values of permeability and selectivity. However, simulation has permitted to correlate accurately permeability and selectivity with the accessible free volume to probes of different radii.

Aromatic polyimides and copolyimides containing bulky t-butyltriphenylmethane units

Triphenylmethane-based polyimides and copolyimides containing bulky t-butyl group (tBu) were obtained by one-step high temperature polycondensation of 2,2′-bis-(3,4-dicarboxyphenyl) hexafluoropropane dianhydride with diamines of triphenylmethane (TPM) family. The polymers were obtained in quantitative yields with inherent viscosities of 0.45–0.80 dL/g. They exhibited high thermal stability with 5% weight loss above 500 °C and were cast in films with good mechanical properties capable of testing as gas separation membranes. All polyimides were readily soluble in polar aprotic solvents, and the solubility enhanced with the increase in tBu-group content. The amorphous, free-standing membranes were prepared from these polymers, and their permeabilities and selectivities to several gases were measured and discussed with respect to the structural differences in the polymers. It was shown that the presence of bulky tBu-units made the chain packing less efficient; free volume and d-spacing in the polyimides grew accordingly. As a consequence, the membranes with higher content of tBu-groups demonstrated improved permeabilities, showing 1.5–3.0 times higher permeability coefficients depending on the gas tested. The membranes’ separation performance was improved for CO2/CH4 gas pair in comparison with that of structurally similar polyimides, while it did not change for O2/N2 pair. Additionally, the mechanism of formation of triphenylmethane diamines in the reaction between aniline and benzaldehydes was investigated in order to optimize the monomer synthesis and to minimize possible side reactions. It was established that the secondary diamines, so-called aminals, were inevitable side products, particularly important in the condensation between aniline and tBu-benzaldehyde.

Moisture-resistance, mechanical and thermal properties of polyimide aerogels

Cross-linked polyimide aerogel has excellent mechanical properties, heat insulation and flame retardancy, but it is easy to absorb water in a humid environment, causing its structure to collapse and deformation, which greatly limits the application of the materials. In this study, a flexible monomer 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FAPB) is introduced into the 4,4′-oxydianiline(ODA)/3,3′,4,4′-biphenyltetracarboxylic dianhydride(BPDA) framework structure, which greatly improve the moisture resistance of the aerogel. The polyimide aerogel obtained by replacing 37.5 mol% of 6FAPB with ODA has water absorption rate as low as 9.5% and water contact angle of 112°. It is found that the aerogel containing 37.5 mol% of 6FAPB do not change significantly after water absorption. In addition, the mechanical properties of polyimide aerogels are also improved, the elongation at break increased from 39.7 to 64.7%. At the same time, the prepared aerogel has good dielectric properties, which greatly improves the range of applications for the aerogels.

Colorless Semi-Alicyclic Copolyimides with High Thermal Stability and Solubility.

A series of colorless copolyimide films with high thermal stability and good solubility are synthesized from (trifluoromethyl)biphenyl-4,4’-diamine (TFMB) with different 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA) to 2,2-bis(3,4-dicarboxyphenyl)-hexafluoropropane (6FDA) dianhydride mole ratios through one-pot solution polycondensation. These copolyimide films exhibit excellent optical transparency (T400 > 90% and λ0 ~305–333 nm) with a thickness of 15 μm and good solubility in most organic solvents. The excellent optical properties are mainly attributed to the low inter- and intra-molecular charge transfer interactions due to the alicyclic structure and the strong electronegative CF3 groups. The glass transition temperature increases from 332 to 352 °C with increasing HPMDA content in the copolymers, while the thermal decomposition temperature is improved with increasing 6FDA content. These results indicate that the copolyimide films can be successfully utilized in the development of novel heat-resistant plastic substrates for the optoelectronic engineering applications.

Thermally rearranged (TR) HAB-6FDA nanocomposite membranes for hydrogen separation

Thermally rearranged (TR) polymers exhibited a good balance of high permeability and high selectivity. For this purpose HAB-6FDA polyimide was synthesized from 3,3 dihydroxy-4,4-diamino-biphenyl (HAB) and 2,2-bis-(3,4-dicarboxyphenyl) hexafluoro propane dianhydride (6FDA) by chemical imidization. Initially, the sample was modified from pure polymer to silica nanofiller doped polymer membrane. Further the modification was done by thermal rearrangement reaction at 350 °C temperature. This modification causes a mass loss in polymer structure and therefore enhances the fractional free volume (FFV). The gases used for the permeation test were H2, CO2, N2 and CH4. Selectivity was calculated for H2/CO2, H2/N2 and H2/CH4 gas pairs and plotted in the Robeson's 2008 upper bound and compared with reported data. The transport properties of these gases have been compared with the unmodified membrane. Permeability of all the gases has increased to that of unmodified polymer membrane. Thermally rearranged polymer nanocomposite exhibits higher gas permeability than that of silica doped and pure polymer. Also the selectivity for H2/CO2 and H2/N2 gas pairs exceeds towards Robeson's upper bound limit. It crosses this limit dramatically for H2/CH4 gas pair. Polymer nanocomposite can be utilized to obtain high purity hydrogen gas for refinery and petrochemical applications.

Preparation and characterization of highly hydrophobic fluorinated polyimide aerogels cross-linked with 2,2′,7,7′-Tetraamino- 9,9′-spirobifluorene

Highly hydrophobic fluorinated polyimide aerogels were successfully prepared using a mild sol-gel method at room temperature from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA), 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,2′-bis(trifluoromethyl)- 4,4′-diaminobiphenyl (TFDB), and cross-linked with 2,2′,7,7′-tetraamino-9,9′-spirobifluorene (TASBF). The obtained polyimide aerogels had low bulky density (0.118–0.161 g/cm3), high specific surface areas (440.6–606.7 m2/g), small pore diameter (17.08–44.89 nm) and excellent mechanical property. These polyimide aerogels also exhibited high thermal stability in both nitrogen and air atmosphere, and the 5% weight loss occurred at temperatures above 530 °C. The introduction of 6FDA into polymer structures enhanced the hydrophobicity of the prepared polyimide aerogels. After replacing 50 mol % of BPDA with 6FDA in the oligomer backbone, water contact angles of the aerogels increased from 104.5° to 126.5°, and water absorption decreased from 4.3% to 2.1%. The high hydrophobicity makes these polyimide aerogels good candidates for use as thermal insulators in harsh environments and other applications.

Transparent, High Glass-Transition Temperature, Shape Memory Hybrid Polyimides Based on Polyhedral Oligomeric Silsesquioxane

Optically transparent polyimides with excellent thermal stability and shape memory effect have potential applications in optoelectronic devices and aerospace industries. A series of optically transparent shape memory polyimide hybrid films are synthesized from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,2′-bis-(trifluoromethyl)biphenyl-4,4′-diamine (TFMB) with various polyhedral oligomeric silsesquioxane (POSS) contents and then subjected to thermal imidization. The hybrid films show good optical transparency (>80% at 400 nm and >95% at 500 nm) with cutoff wavelengths ranging from 318 to 336 nm. Following the incorporation of the inorganic POSS structure, the hybrid films exhibit excellent thermal stability with glass transition temperature (Tg) ranging from 351 to 372 °C. The hybrid films possess the highest Tg compared with the previously-reported shape memory polymers. These findings show that POSS is successfully utilized to develop transparent polyimides with excellent thermal stability and shape memory effect.

Self-Healing Anti-Atomic-Oxygen Phosphorus-Containing Polyimide Film via Molecular Level Incorporation of Nanocage Trisilanolphenyl POSS: Preparation and Characterization.

Protection of polymeric materials from the atomic oxygen erosion in low-earth orbit spacecrafts has become one of the most important research topics in aerospace science. In the current research, a series of novel organic/inorganic nanocomposite films with excellent atomic oxygen (AO) resistance are prepared from the phosphorous-containing polyimide (FPI) matrix and trisilanolphenyl polyhedral oligomeric silsesquioxane (TSP–POSS) additive. The PI matrix derived from 2,2’-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and 2,5-bis[(4-amino- phenoxy)phenyl]diphenylphosphine oxide (BADPO) itself possesses the self-healing feature in AO environment. Incorporation of TSP–POSS further enhances the AO resistance of the FPI/TSP composite films via a Si–P synergic effect. Meanwhile, the thermal stability of the pristine film is maintained. The FPI-25 composite film with a 25 wt % loading of TSP–POSS in the FPI matrix exhibits an AO erosion yield of 3.1 × 10−26 cm3/atom after an AO attack of 4.0 × 1020 atoms/cm2, which is only 5.8% and 1.0% that of pristine FPI-0 film (6FDA-BADPO) and PI-ref (PMDA-ODA) film derived from 1,2,4,5-pyromellitic anhydride (PMDA) and 4,4’-oxydianline (ODA), respectively. Inert phosphorous and silicon-containing passivation layers are observed at the surface of films during AO exposure.

Optical, thermal and gas separation properties of acetate-containing copoly(ether-imide)s based on 6FDA and fluorenyl diamines

The diamine, 9,9-bis[4-(4-amino-3-hydroxylphenoxy)phenyl]fluorene (BAHPPF) was synthesized by the modified two-step method. Then, a series of acetate-containing copoly(ether-imide)s were prepared by the copolymerization of BAHPPF, 9,9-bis(4-aminophenyl)fluorene (BAF) and 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) followed by chemical imidization. The structures and properties of the BAHPPF and copoly(ether-imide)s were characterized by nuclear magnetic resonance spectrometer (NMR), Fourier transform infrared spectrometer (FTIR), X-ray diffractometer (XRD), differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), ultraviolet-visible spectrophotometer (UV-VIS), and tensile testing. Single gas permeation performances of these copoly(ether-imide)s were also studied for five representative gases of interest including H2, O2, N2, CO2, and CH4. The experimental results showed that the copoly(ether-imide)s showed excellent optical properties with high light transmittance above 80.2% at 450 nm. The glass transition temperature of these copolymers were higher than 333°C. Their tensile strength and Young’s module also increased, and the elongation decreased with the decrease of BAHPPF. High gas permeabilities of copoly(ether-imide)s were obtained, and the ideal selectivity of CO2/CH4 was improved due to the introduction of acetate group and flexible ether linkage. These copoly(ether-imide)s could be applied to the field of optics and gas separation.

Associative behavior of polyimide/cyclohexanone solutions.

Our previous work has demonstrated that soluble polyimide with relatively weak interaction can be transformed from neutral polymer to associative polymer by increasing molecular weight. Thus, it is necessary to find another way to vary the relatively weak interaction strength, i.e. variation of solvent quality. Herein, viscoelastic behaviors are examined for 2,2-bis(3,4-dicarboxy-phenyl) hexafluoropropane dianhydride (6FDA)-2,2′-bis(trifluoromethyl)-4,4′-diam (TFDB) polyimide (PI), with a relatively low molecular weight (Mw) of 88 000 g mol−1, dissolved in cyclohexanone (CYC). The scaling relationship between viscosity (η0–ηs) and volume fraction is in good agreement with the associative polymer theory proposed by Rubinstein and Semenov. Oscillatory rheological results indicate that the PI solution tends to become a gel with increased volume fraction. The synchrotron radiation small-angle X-ray scattering results imply the existence of dense aggregates in the concentrated PI/CYC solutions. Shear thickening and thinning behaviors are observed in the solutions, and the shear thickening behavior of polyimide solution has not been reported in literature. Their mechanisms are studied by conducting dynamic and steady rheological experiments. Thus, enhancing the relatively weak interaction strength can also make the low Mw polyimide show associative polymer behavior. This work can help us to gain deep insight into polyimide solution properties from dilute to semidilute entangled solutions, and will guide the preparation of polyimide solutions for different processing.