Physical and Gas Transport Properties of Novel Hyperbranched Polyimide – Silica Hybrid Membranes

Summary Physical and gas transport properties of novel hyperbranched polyimide – silica hybrid membranes were investigated. Hyperbranched polyamic acid as a precursor was prepared by polycondensation of a triamine monomer, 1,3,5-tris(4-aminophenoxy)benzene (TAPOB), and a dianhydride monomer, 4,4-(hexafluoro-isopropylidene)diphthalic anhydride (6FDA), and subsequently modified the end groups by 3-aminopropyltrimethoxysilane (APTrMOS). The hyperbranched polyimide – silica hybrid membranes were prepared using the polyamic acid, water, and tetramethoxysilane (TMOS) via a sol-gel technique. 5 % weight-loss temperature and glass transition temperature of the hyperbranched polyimide – silica hybrid membranes determined by TG-DTA measurement considerably increased with increasing silica content, indicating effective cross-linking at polymer – silica interface mediated by APTrMOS moiety. CO₂, O₂, and N₂ permeability coefficients of the hybrid membranes increased with increasing silica content. It was pointed out that the increased gas permeabilities are mainly attributed to increase in the gas solubilities. On the contrary, CH₄ permeability of the hybrid membranes decreased with increasing silica content because of decrease in the CH₄ diffusivity and, as a result, CO₂/CH₄ selectivity of the hybrid membranes remarkably increased. It was concluded that the 6FDA-TAPOB hyperbranched polyimide – silica hybrid membranes have high thermal stability and excellent gas selectivity, and are expected to apply to a high-performance gas separation membrane.     

Synthesis,characterization, and CO2 permeation properties of acetylene‐terminated polyimide membranes

A novel fluorine‐containing telechelic polyimide end‐capped with acetylene group which derived from 4,4‐(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,4‐diaminodiphenyl ether (DADE), and 4‐(2‐phenylethynyl) phthalic anhydride (PEPA) was synthesized using polycondensation. The physical and CO₂ permeation properties of its crosslinked membranes prepared by the cyclotrimerization reaction of the acetylene groups at the polymer chain end using tantalum (V) chloride (TaCl₅) as a catalyst under thermal treatment was investigated in terms of CO₂‐induced membrane plasticization. The crosslinked membranes showed a gel content in organic solvent, which was good solvent of noncrosslinked membranes, and improved their thermal stability. Based on the measurement of the high‐pressure time dependence on CO₂ permeation, the crosslinked 6FDA–DADE–PEPA membranes exhibited more resistance to CO₂‐induced plasticization than noncrosslinked 6FDA–DADE and thermal treated 6FDA–DADE–PEPA. Furthermore, the increase in TaCl₅ content resulted in more resistance to plasticization. The cyclotrimerization reaction of the acetylene groups at the polymer chain ends using a transition metal catalyst under thermal treatment was found to be more effective than conventional thermal treatments for suppressing membrane plasticization without the membrane densification. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Enhancement of physical properties of electroactive polyimide nanocomposites by addition of graphene nanosheets

Electroactive polyimide (EPI) nanocomposites with amino‐capped aniline trimer and 4′‐(4,4′‐isopropylidene‐diphenoxy)bis(phthalic anhydride) as monomers, and functionalized with carboxyl‐graphene nanosheets, were prepared by thermal imidization. The as‐prepared electroactive polyimide/graphene nanocomposite (EPGN) materials were then characterized by Fourier transform infrared spectroscopy and transmission electron microscopy. In situ monitoring of the redox behavior of the as‐prepared EPGN materials was performed by cyclic voltammetry studies. The effects of material composition on the mechanical, thermal, thermal transport, dielectric and molecular barrier properties of EPGN membranes were investigated by dynamic mechanical analysis, TGA, DSC, the transient plane source technique, LCR meter and gas permeability analyzer, respectively. It should be noted that all the properties of the EPGN membranes were found to improve substantially over those of non‐electroactive polyimide and EPI. For example, upon loading of 1 wt% graphene, EPGN membranes were found to have an increase of over 20%, 5%, 65% and 20% in mechanical strength, thermal stability, thermal conductivity and dielectric constant, respectively, and a reduction of over 20% in gas permeability. © 2013 Society of Chemical Industry     

Preparation and properties of (BATB–ODPA) polyimide–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of 1,4‐bis(4‐aminophenoxy)‐2‐tert‐butylbenzene–4,4′‐oxydiphthalic anhydride (BATB–ODPA) polyimide (PI) and layered montmorillonite (MMT) clay were successfully prepared by an in situ polymerization reaction through thermal imidization up to 300°C. The synthesized PCN materials were subsequently characterized by Fourier‐Transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of material composition on thermal stability, mechanical strength, molecular permeability and optical clarity of bulk PI and PCN materials in the form of membranes were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), molecular permeability analysis (GPA) and ultraviolet‐visible (UV/VIS) transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1072–1079, 2004     

Effect of propyleneimine external cross-linker on the properties of acrylate latex pressure sensitive adhesives

Acrylate pressure sensitive adhesive (PSA) latexes were synthesized via a starved monomer seeded semi-batch emulsion polymerization process with butyl acrylate (BA), methyl methacrylate (MMA), acrylic acid (AA) and 2-hydroxyethyl acrylate (HEA). These PSA polymers were then cross-linked with trifunctional propyleneimine external cross-linker (SAC-100) to study the cross-linking reaction between carboxylic group of the polymer chain and cross-linking agent. It was found that cross-linking provided a significant influence on the film formation process based on the result of SEM analysis. In addition, with the increase of SAC-100 content, the gel content of the polymer increased significantly, while molecular weight between cross-link points (M_c) and the sol molecular weight (M_w, M_n) of the polymer decreased remarkably. The TGA result showed that the addition of the external cross-linker can enhance the thermal stability of the latex film. Moreover, for the cross-linked adhesive film, the shear strength was improved greatly while at the sacrifice of loop tack and peel strength, when compared with the uncross-linked counterparts. Besides, dynamic mechanical analysis (DMA) was also used to evaluate the viscoelastic properties of the acrylate emulsion PSA film.     

Characterization and thermal degradation of polyimides derived from ODPA and several alicyclic‐containing diamines

Thermal properties of polyimides with main chain containingalicyclic units derived from 3,3′ 4,4′‐oxydiphthalic anhydride (ODPA) and several alicyclic‐ containing diamine monomers, including 1,4‐bis (4‐aminophenoxymethylene) cyclohexane (BAMC), 1,4‐bis (3‐aminophenoxymethylene) cyclohexane (mBAMC), 1,4‐bis (4‐aminobenzoyoloxymethyl) cyclohexane (BAZMC), and 1,4‐bis (3‐aminobenzoyoloxymethyl) cyclohexane (mBAZMC) were characterized in detail. The thermal stability, apparent activation energy, and evolved gas analysis of these polyimides were done using thermogravimetric analysis (TGA) coupled with Fourier transform infrared (FTIR) spectroscopy. Experimental results indicated that the resulting polyimides showed fairly high thermal stability, no weight loss was detected before a temperature of 400°C in nitrogen, and the values of glass‐transition temperature of them were in the range of 134–181°C. Activation energy for the initial thermal degradation of polyimide derived from ODPA and mBAMC in nitrogen were 166 and 162 kJ/mol in two different methods. The TG‐IR results represented that the major evolved products from the nonoxidative thermal degradation were detected to be hydrocarbons, CO, CO₂, H₂O, and aromatic compounds. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

新型侧链型聚酰亚胺膜的制备及其渗透汽化分离性能

针对苯/环己烷混合物体系的特点,采用两种新型侧链二胺3,5-二氨基苯甲酸苯酯(PDA)和3,5-二氨基苯甲酸-4-三氟甲基苯酯(FPDA),制备了一系列由不同二酐与二胺单体如4,4'-二氨基二苯醚(ODA)和3,5-二氨基苯甲酸(DABA)聚合而成的用于渗透汽化分离苯/环己烷的聚酰亚胺膜,对其结构和各项性质进行了表征,并对膜材料的微观结构与宏观分离性能之间的关系进行了较为深入的研究。随着侧链二胺的引入,聚酰亚胺膜的分离效率随之持续增大,分离能力得以改善。渗透汽化实验结果表明,以6FDA为二酐单体的两类聚酰亚胺膜具有较优异的分离性能。乙二醇交联的6FDA-FPDA/ODA/DABA(1:7:2)膜综合渗透汽化分离性能最优。在50℃时,对于含苯50 %(质量)的苯/环己烷混合物,其渗透通量为9.84 kg·μm·m^-2·h^-1,分离因子达6.1。     

Synthesis and characterization of rubbery/glassy blend membranes for CO<Subscript>2</Subscript>/CH<Subscript>4</Subscript> gas separation

A series of blend membranes made from the rubbery polyether block amide (Pebax®1657) and a glassy polymer, polyethersulfone (PES) or Matrimid 5218, were fabricated by solution casting with different ratios (10–40 %), in order to combine high permeability of the former with high selectivity of the latter polymer for CO₂/CH₄ gas separation. The membranes were characterized by scanning electron microscopy (SEM), differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR), and stress–strain tests. These blend membranes showed two distinct T _g s, indicating their immiscible nature as confirmed by SEM images. However, weak intermolecular interaction between polymers, as illustrated by the FTIR results, corresponds to some degree to their compatibility and improved mechanical strength, compared to the pure Pebax®. TGA analysis revealed that addition of glassy polymer improved membranes’ thermal stability. Effect of feed pressure on membrane separation, investigated by three different pressures (4, 8, and 12 bar), indicated increased permeability for higher pressures for both CO₂ and CH₄. Gas separation tests also pointed to improved separation properties of the blend membranes compared to those of the neat polymers, prepared the same way.     

Preparation of thermal stable porous polyimide membranes by phase inversion process for lithium-ion battery

The porous polyimide membranes were prepared by a wet phase inversion process based on the organo-soluble polyimide. The influence of coagulation bath composition and casting polymer solution concentration on the morphology of membranes was investigated. A series of spongy-like porous polyimide membranes with different porosity were obtained and characterized. These porous polyimide membranes exhibited excellent thermal stability and dimensional stability with the glass transition temperature of 274 °C and thermal shrinkage less than 1% after stored at 200 °C. All the porous polyimide membranes exhibited good wettability with electrolyte uptake of 190–378% due to their high surface polarity and high porosity. The discharge curves for the lithium-ion cells using porous polyimide membranes as separator displayed relatively flatter voltage plateaus than that for Celgard 2400 membrane and gave the discharge capacity of 129–131 mAh/g. The thermal stable porous polyimide membranes are favorable to be applied as separator in the lithium-ion cell and can be expected to provide excellent battery performance at elevated temperature.     

聚酰亚胺膜气体渗透性的改性进展

聚酰亚胺分离膜(PI)是由芳香二酐和二胺单体缩聚而成的,它是主链含有酰亚胺环的一类高聚物。因其具有良好的气体分离性能、热稳定性、耐溶剂性等特性而受到人们的广泛关注。但是,其气体渗透-选择性的平衡问题限制了其在气体分离领域的广泛应用。因此,研究者们将目光转向了聚酰亚胺膜气体渗透性的改性方面,使其具有良好的气体渗透性,用于混合气体的高效分离。文章综述了近年来研究者对聚酰亚胺气体渗透性的研究进展,详细介绍了共混改性、交联改性和分子结构改性方面的最新研究成果,并总结展望了聚酰亚胺膜今后的研究趋势。为未来高效分离膜的研发提供了参考。     

Soluble aromatic polyimides based on 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane: Synthesis and properties

Aromatic polyimides were synthesized from 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6F-OH diamine) and different aromatic dianhydrides by a one-step hightemperature polycondensation, or by a two-step procedure using either thermal or chemical imidization of poly(amic acids), PAA. The obtained polyimides were compared in terms of their chemical structure, molecular weight, mechanical and thermal properties. The reaction of 6F-OH diamine with different aromatic dianhydrides in amide solvents at room temperature resulted in the formation of PAA with moderate molecular weight (η_inh ⩽ 0.7 g/dL). The thermal imidization of these PAAs led to brittle hydroxy polyimides (PI-6F-OH). In contrast, chemical imidization of similar PAAs in acetic anhydride and pyridine brought about flexible self-supporting polyimide films. The FTIR analysis indicated that the latter process was accompanied by an esterification of the OH groups in the diamine moieties, resulting in the formation of the polymers with side acetate groups (PI-6F-Ac). The high molecular weight hydroxy polyimides, suitable for preparation of films with good tensile properties, were synthesized by a one-step high-temperature polycondensation in phenolic solvents. All obtained polyimides were well soluble in common organic solvents. The highest solubility was observed for PI-6F-Ac. It was found by means of FTIR and TGA that the polyimides with the R group (R = OH or acetate) in orto position to the nitrogen atom in the diamine moiety underwent a rearrangement to benzoxazoles above 300°C. The starting temperature and conversion of this rearrangement reaction were controlled by the type of R group. The imide-to-benzoxazole rearrangement shifted to lower temperatures, and higher conversion was encountered for the polyimides with side acetate group, PI-6F-Ac, obtained by chemical imidization. © 1996 John Wiley & Sons, Inc.     

Effects of functional groups on the thermal properties of modified polystyrene

Polystyrene is, after polyolefins, the most widespread polymer in both industry and everyday life, successfully replacing some raw natural materials. In this study, the chemical modification of polystyrenes of different molecular weights was performed with various functional group modifiers (epichlorohydrin, maleic anhydride, and acetic anhydride) in one stage and in the medium of the cationic catalyst BF₃·O(C₂H₅)₂ according to previous studies. The concentration of the functional groups bonded to the aromatic ring of the polymer as a result of the chemical modification of polystyrenes of different molecular weights depended on the molecular weight of the polymer, and more functional groups were bonded to lower molecular weight polystyrene. The effects of the functional groups bonded to the structure of the polymer on the thermal properties of modified polystyrene were investigated. The polystyrene that was modified by maleic anhydride was more stable against thermal destruction at high temperatures. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2549–2553, 2007     

Influence of melt stability on the crystallization of bis(4-aminophenoxy)benzene-oxydiphthalic anhydride based polyimides

Novel high performance semicrystalline polyimides, based on controlled molecular weight phthalic anhydride (PA) endcapped 1,4-bis(4-aminophenoxy)benzene (TPEQ diamine) and oxydiphthalic dianhydride (ODPA), were synthesized. They exhibited excellent thermal stability in nitrogen and air atmospheres as determined by thermogravimetric analysis (TGA). The glass transition temperatures (T_g) for these polymers ranged from 225°C for the 10,000 M_n (10K) polymer, to 238°C for the 30,000 (30K) M_n material. The observed melting temperatures for all the polymers were ∼420°C. The crystallization behavior of these polymers showed a strong molecular weight dependence, as illustrated by the observation that the 10K and 12.5K polymers crystallized with relative ease, whereas the 15K, 20K, and 30K polymers showed little or no ability to undergo thermal recrystallization. The thermal stability of these polymers above T_m was investigated by studying the effect of time and temperature in the melt on the cold crystallization and melting of these polymers. Increased time and temperature in the melt resulted in lower crystallinity because of melt state degradation, such as crosslinking and branching, as evidenced by an increase in melt viscosity, which was more prominent for the higher molecular weight polymers.     

PA封端型聚酰亚胺的合成与表征

以均苯四甲酸二酐(PMDA)和自制的1,3-双(4-氨基苯氧基)苯(TPER)在邻苯二甲酸酐(PA)封端的情况下溶液缩聚得到聚酰胺酸(PAA),通过溶液亚胺化和固相亚胺化相结合得到聚酰亚胺(PI).用傅立叶变换红外光谱仪、乌氏粘度计和热失重分析仪对PI进行了结构表征和性能测试,分析了封端剂加入量、亚胺化方式对PI性能的影响.结果表明,封端剂的加入可有效降低PI的粘度,两种亚胺化方式的结合可以降低PI的最终亚胺化温度,得到的PI热稳定性高.     

New highly proton-conducting membrane poly(vinylpyrrolidone)(PVP) modified poly(vinyl alcohol)/2-acrylamido-2-methyl-1-propanesulfonic acid (PVA-PAMPS) for low temperature direct methanol fuel cells (DMFCs)

A new type of chemically cross-linked polymer blend membranes consisting of poly(vinyl alcohol) (PVA), 2-acrylamido-2-methyl-1-propanesulfonic acid (PAMPS) and poly(vinylpyrrolidone) (PVP) have been prepared and evaluated as proton conducting polymer electrolytes. The proton conductivity (σ) of the membranes was investigated as a function of cross-linking time, blending composition, water content and ion exchange capacity (IEC). Membranes were also characterized by FT-IR spectroscopy, thermogravimetric analysis (TGA), and the differential scanning calorimetry (DSC). Membrane swelling decreased with cross-linking time, accompanied by an improvement in mechanical properties and a small decrease in proton conductivity due to the reduced water absorption. The membranes attained 0.088 S cm⁻¹ of the proton conductivity and 1.63 mequiv g⁻¹ of IEC at 25±2 °C for a polymer composition PVA-PAMPS-PVP being 1:1:0.5 in mass, and a methanol permeability of 6.1×10⁻⁷ cm² s⁻¹, which showed a comparable proton conductivity to Nafion 117, but only one third of Nafion 117 methanol permeability under the same measuring conditions. The membranes displayed a relatively high oxidative durability without weight loss of the membranes (e.g. 100 h in 3% H₂O₂ solution and 20 h in 10% H₂O₂ solution at 60 °C). PVP, as a modifier, was found to play a crucial role in improving the above membrane performances.     

Synthesis and characterization of soluble polyimides and its ultrafiltration membrane performances

Soluble polyimides were synthesized and characterized from two diamines and four dianhydrides by the two- and the one-step method. Most of the polyimides could be soluble by one-step method except α,α′-bis(4-aminophenyl)-1,4-diisopropyl benzene/3,3′,4,4′-benzophenonetetracarboxylic dianhydride system in limited organic solvents. Glass transition temperatures ranged from 186 to 233°C and crystalline melt temperatures were not observed. All the soluble polyimides showed good thermal, mechanical, and electrical properties. The polyimides did not have crystalline structure and limited solubilities. The effective solvent had a medium dispersion component associated with weak polar and hydrogen components. The polymer from one-step polymerization had a narrower molecular weight distribution than the two-step method. Polyimide synthesized with 4,4′-oxydiphthalic anhydride and bis[4-(3-aminophenoxy)phenyl]sulfone by two-step method could only be prepared by the typical phase inversion method. Other membranes except this polyimide membrane could not be prepared by the typical phase-inversion method because of poor solubility about polar solvents. The flux of this ultrafiltration membrane was very high, and this membrane could especially retain polymer having a molecular weight 20,000 to above 90%. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 907–918, 1999     

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

The 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 Properties of Cyano-Containing Polyimide Films Based on 2,6-Bis(4-aminophenoxy)- benzonitrile

Summary A series of cyano-containing polyimides were synthesized from 2,6-bis(4-amino- phenoxy)benzonitrile and some aromatic dianhydride monomers by solution polycondensation. The poly(amic acid) films could be obtained by solution-cast from N-methyl-2-pyrrolidinone solutions and thermally converted into tough polyimide films. Structure and physical properties of thin films of those polyimides were measured by FTIR, TGA, dynamic mechanical analysis and LCR hitester et al. Results showed that the polyimides prepared from 2,6-bis(4-aminophenoxy)- benzonitrile and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride or 4,4’-(hexafluoropropylidene)diphthalic anhydride exhibited more excellent energy-damping characteristic and excellent solubility in NMP, DMF, DMAc, DMSO, THF and CHCl₃, whereas the polyimides from 2,6-bis(4-aminophenoxy)benzonitrile and 3,3’,4,4’-biphenyltetracarboxylic dianhydride or Pyromellitic dianhydride were insoluble in polar and nonpolar organic solvents. All polyimides indicated higher glass transition temperatures, excellent thermal stability and tensile properties. Incorporating a nitrile group into the polyimide backbone would enhance the dielectric constant of the polyimide films.     

Preparation and characterization of high‐temperature resistance polyimide foams

A new high‐temperature resistance polyimide foam was synthesized from 2,3,3′,4′‐biphenyltetracarboxylic dianhydride (α‐BPDA) and p‐phenylenediamine (p‐PDA). The structures and foaming process of polyimide precursor powders were characterized by wide‐angle X‐ray diffractometer (WXRD) and the self‐made visualization device, respectively. The imidization degree, thermal mechanical properties and thermal stability of the polyimide foams with different post‐treatment temperatures were also measured by fourier transform infrared spectrometer spectrum (FTIR), dynamic thermal mechanical anaylsis (DMTA), and thermogravimetric analysis (TGA). Results showed that the inflation onset temperatures of polyimide precursor powders ranged from 122 to 135°C with varying the heating rate. And the increase in the imidization degree, glass transition temperatures (T_g) and temperatures for 5 wt% mass loss of high‐temperature resistance polyimide foams can be achieved with increasing post‐treatment temperature. It was quite surprising to find that T_g of high‐temperature resistance polyimide foam post‐treated at 420°C was up to above 450°C, and the char yield at 800°C was more than 60%. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Thermal characteristics and pyrolysis of methyl‐di(phenylethynyl)silane resin

Thermal stability of a recently synthesized polymeric methyl‐di(phenylethynyl)silane (MDPES) resin was studied using a number of thermal and spectrometric analytical techniques. The polymer exhibits extremely high thermal stability. Thermogravimetric analysis (TGA) shows that the temperature of 5% weight loss (T_d5) was 615°C and total weight loss at 800°C was 8.9%, in nitrogen atmosphere, while in air, T_d5 was found to be 562°C, and total weight loss at 800°C was found to be 55.8% of the initial weight. Differential thermal degradation (DTG) studies show that the thermal degradation of MDPES resin was single‐stage in air and two‐stage in nitrogen. The thermal degradation kinetics was studied using dynamic TGA, and the apparent activation energies were estimated to be 120.5 and 114.8 kJ/mol in air, respectively, by Kissinger and Coats–Redfern method. The white flaky pyrolysis residue was identified to be silicon dioxide by FTIR and EDS, indicating that the thermal stability of polymer may be enhanced by the formation of a thin silicon dioxide film on the material surface. © 2006 Wiley Periodicals, Inc. J Appl PolymSci 103: 605–610, 2007