Preparation and performance of a novel polyimide foam

A new type of polyimide foam (PIF) was prepared and characterized based on a one‐pot process by the reaction of a first solution with different ratios of a second solution. The first solution was comprised of pyromellitic dianhydride (PMDA), N, N‐dimethyl formamide (DMF), methanol, water, surfactant, and catalysts, while the second solution contained polyaryl polymethylene isocyanate (PAPI). In the present study, the relationships among compositions, structures, and properties of PIFs were investigated. The results indicated that with the increase in the weight ratio of PAPI/(first solution), the foaming degrees of PIFs increased from 10.14 to 10.52 times and the apparent densities before postcure decreased from 15.96 to 14.51 kg/m³. The open cell contents, average sound absorption coefficients, and average cellular diameters of PIFs after postcure increased with increase in the weight ratio of PAPI/(first solution). The glass transition temperatures (T_g) of PIFs after postcure first increased from 287 to 299°C, then decreased to 292°C, and the 5% weight loss temperatures and 10% weight loss temperatures presented the same trend as well. The compressive and flatwise tensile properties scaled very well with the relative densities of the foams after postcure, with the highest compressive strength of 0.03 MPa and the highest flatwise tensile strength of 0.15 MPa. Copyright © 2011 John Wiley & Sons, Ltd.     

Chain Conformation and Local Rigidity of Soluble Polyimides(Ⅱ): Isomerized Polyimides in THF

Two soluble isomerized polyimides(PIs)synthesized from 2,2′-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride(6FDA)with either 2,2′-dimethylbenzidine(2,2′-DMB)or 3,3′-DMB were investigated by means...     

Sorption and diffusion of water vapor in polyimide films

Sorption and diffusion of water vapor are investigated gravimetrically for polyimide films. The activity dependence of the solubility and diffusion coefficients, S and D, respectively, is classified under four types: (1) constant S and D type, (2) dual-mode sorption and transport type, (3) dual-mode type followed by a deviation due to a plasticization effect at high vapor activity, and (4) constant S and D type followed by a deviation due to water cluster formation at high activity. For the dual-mode type, the Henry's law component is much larger than the Langmuir component except at low activity, and therefore deviation in behavior from the first type is small. S is larger for polyimides with higher content of polar groups such as carbonyl, carboxyl, and sulfonyl. D is larger for polyimides with a higher fraction of free space, with some exceptions. The polyimide from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and dimethyl-3,7-diaminodibenzothiophene-5, 5-dioxide belongs to the third type and displays both large S and large D. The polyimide from 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride and 4,4′-oxydianiline belongs to the fourth type, and has the largest D but rather small S because of the hydrophobic C(CF₃)₂ groups. © 1992 John Wiley & Sons, Inc.     

Assessment of the Nature of Depolarization Current in Thermally Treated Kapton Polyimide

Pyrolysis of normally insulating aromatic polyimide is known to impart electrical conductivity to the polymer due to the formation of carbonized regions in an insulating matrix with a concomitant change in the polymer’s structural arrangement. The wholly pyrolyzed polyimide is potentially useful for specific applications in certain types of semiconductor devices because of the polyimide’s insulator/conductor transition which creates a barrier type conduction. Pyrolysis, however, degrades the required mechanical integrity of the polyimide for construction of such devices. In order to evaluate the fundamental aspects of barrier conduction by high voltage electron transfer from metal contact that can still produce measurable current in thermally treated non-pyrolyzed polyimide, the nature of depolarization in Kapton was assessed by the thermally stimulated depolarization current (TSDC) technique. The results show that thermal treatment of polyimide without pyrolysis and therefore without loss of mechanical integrity offers a viable means of steady electron conduction for semiconductor operation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polymerization and nanocomposites properties of multifunctional methylmethacrylate POSS

Thermally induced polymerization of multifunctional methylmethacrylate POSS (MMA‐POSS) was studied in this work for preparation of polymer/POSS nanocomposites. The polymerization of MMA‐POSS could be promoted with benzoyl peroxide (BPO). Self‐assembly of POSS into a layer‐by‐layer structure in the MMA‐POSS polymer (TP‐MMA‐POSS) is observed with a transmission electron microscopy. An ultra‐low‐k value of about 1.85 is measured with TP‐MMA‐POSS. In addition, polyimide‐POSS nanocomposites are also prepared. These nanocomposites demonstrate good homogeneity and enhanced mechanical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5157–5166, 2008     

Direct patterning of poly(amic acid) and low‐temperature imidization using a crosslinker,a photoacid generator,and a thermobase generator

A positive‐type photosensitive polyimide (PSPI) based on poly(amic acid) (PAA), a crosslinker 1,1,1‐tris{4‐[2‐(vinyloxy)ethoxy]phenyl}ethane (TVPE), a photoacid generator (PAG) (5‐propylsulfonyloxyimino‐5H‐thiophen‐2‐ylidene)‐2‐(methylphenyl)acetonitrile (PTMA), and a thermobase generator (TBG) t‐butyl 2,6‐dimethylpiperidine‐1‐carboxylate (BDPC) has been developed as a promising material in microelectronics. The PAA was prepared from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐oxydianiline (ODA) in dimethyl sulfoxide (DMSO). The PSPI, consisting of PAA (69 wt %), TPVE (21 wt %), PTMA (3 wt %), and BDPC (7 wt %), showed high sensitivity of 21 mJ/cm² and a high contrast of 6.8 when it was exposed to a 436‐nm line (g‐line), postbaked at 90 °C for 5 min, and developed with 1.69 wt % TMAHaq. A clear positive image of 8 μm line and space pattern was printed on film, which was exposed to 50 mJ/cm² of g‐line by a contact printing mode and fully converted to the corresponding polyimide (PI) pattern on heating at 200 °C, confirmed by FTIR spectroscopy. Thus, this system will be a good candidate for next generation PSPIs. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3362–3369, 2009     

Preparation and characterization of sulfonated polyimide ionomers via post‐sulfonation method for fuel cell applications

This paper describes our work on the synthesis of a series of sulfonated homo‐/co‐polyimides (SPI) which were obtained by post‐sulfonation method over three steps. In the first step, 4,4′‐oxydianiline (ODA) and 4,4′‐diaminodiphenylsulfone (DDS) dissolved in N‐methyl pyrrolidone (NMP) were reacted with benzophenonetetracarboxylic dianhydride (BTDA) in order to yield poly(amic acid) (PAA). Secondly, precipitated PAA was sulfonated via concentrated sulfuric acid (95–98%) at room temperature to give post‐sulfonated PAA (PSPAA). Finally, PSPAA was converted into post‐sulfonated PI (PSPI) by the thermal imidization method. PSPIs with ion exchange capacity (IEC) ranging from 0.20 to 0.67 meq/g were prepared. The thermal properties of the PSPIs were evaluated and high desulfonation temperature was found in the range of 190–350°C, suggesting the high stability of sulfonic acid groups. In water, PSPI‐5 membrane displayed similar proton conductivity to Nafion®117, whereas this membrane showed poor conductivity in dry state. All PSPIs displayed good solubility in common polar aprotic solvents such as NMP and dimethylacetamide (DMAc). Furthermore, the effects of post‐sulfonation reaction on chemical structure, thermal oxidative behavior, and physical properties of the PSPI membranes such as membrane quality/stability and water uptake were discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Research for improvement on the extract efficiency of lignans in traditional Chinese medicines by hybrid ionic liquids: As a case of Suhuang antitussive capsule

Recently, efficient extraction of natural products from traditional Chinese medicines (TCMs) by green solvents is deemed an essential area of green technology and attracts extensive attentions. In this work, a green protocol for simultaneous ultrasonic-extraction of the native compounds with different polarities of TCMs by using a hybrid ionic liquids (HILs)-water system was reported for the first time. As a case study, three superior ILs (1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]), and 1-allyl-3-methylimidazolium chloride ([AMIM]Cl)) were chosen as the compositions of the HILs system, and the TCMs Suhuang antitussive capsule (SH) containing different-polarity lignans was selected. Primarily, an ultra-performance liquid chromatography coupled to triple quadrupole tandem mass spectrometry (UPLC-QqQ-MS/MS) method in the multiple reaction monitoring (MRM) mode was established for qualitative and quantitative analysis of 18 lignans. After majorization by uniform design experiment, the HILs prepared with [AMIM]Cl, [EMIM][BF4], and [EMIM][OAc] at a volume ratio of 1:5:5 could simultaneously extract multi-polarity lignans compared to single IL. Subsequently, the conditions of ultrasonic extraction employing with HILs and traditional organic solvent were optimized by the response surface methodology, respectively. The results indicated that the extract efficiency of the HILs system for target compounds was significantly improved compared with the traditional organic solvent-extraction, i.e. the content of total lignans in ethanol system was up to 47 mg/g, while that in the HILs system was up to 69 mg/g, with an increasing of 47%. Additionally, ¹H-NMR and ¹³C-NMR spectra were used to characterize the hydrogen-bond interactions in the HILs-lignan mixtures. Extraction with the HILs in TCMs is a new application schema of ILs, which not only avoids the use of volatile toxic organic solvents, but also shows the potential to be comprehensively applied for the extraction of bioactive compounds from TCMs.     

Pattern formation of polyimide by using photosensitive polybenzoxazole as a top layer

A versatile method for positive-type patterning of polyimide (PI) based on a two-layer photosensitive poly(benzoxazole) (PSPBO) and poly(amic acid) (PAA) film has been developed to provide a promising material in the field of microelectronics. This patterning system consisted of a pristine PAA thick bottom-layer and a poly(o-hydroxy amide) (PHA) thin top layer with 9,9-bis[4-(tert-butoxycarbonyl-methyloxy)phenyl]fluorene (TBMPF) as a dissolution inhibitor, and (5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)-acetonitrile (PTMA) as a photoacid generator (PAG). The PHA and PAA were prepared from 4,4′-(hexafluoroisopropylidene)-bis(o-aminophenol) and 4,4′-oxybis(benzoic acid) derivatives, and 3,3′,4,4′-biphenyltetracarboxylic dianhydride and 4,4′-oxydianiline, respectively, in N,N-dimethylacetamide. This two-layer system based on PHA (150-nm thickness) and PAA (1.5-μm thickness) showed high sensitivity of 35 mJ/cm² and high contrast of 10.3 when exposed to a 365 nm line (i-line), post-baked at 100 °C for 2 min, and developed in a 2.38 wt.% tetramethylammonium hydroxide aqueous solution/5 wt.% iso-propanol at 25 °C. A clear positive image of a 4-μm line-and-space pattern was printed on a film which was exposed to 100 mJ/cm² of i-line by a contact-printing mode and fully converted to the corresponding PBO/PI pattern upon heating at 350 °C, confirmed by FT-IR spectroscopy. This two-layer system could be applied to the patterning of various PAAs.     

Polyimide/polyoxometalate copolymer thin films: synthesis,thermal and dielectric properties

A mono‐lancunary keggin‐type decatungstosilicate (SiW₁₁) polyoxometalate (POM) modified by γ‐aminopropyltriethoxysilane (KH550) was incorporated into polyimide (PI) through copolymerization. Nuclear magnetic resonance (NMR), fourier transition infrared spectroscopy (FTIR), and wide angle X‐ray diffraction (WAXD) were used to characterize the structure and composition of the polyoxometalate–organosilane hybrid (SiW₁₁KH550) and PI/SiW₁₁KH550 copolymers. The differential scanning calorimetry (DSC) studies indicate that the glass transition temperature (T_g) of PI/SiW₁₁KH550 copolymers increases from 330°C (for neat PI) to 409°C (for the copolymer sample with 10 wt% of SiW₁₁KH550). Dielectric measurement showed that both the dielectric constant and the dielectric loss for the copolymer thin films decreased with the increase in SiW₁₁KH550 content, and the dielectric constant and dielectric loss values decreased to 2.1 and 3.54 × 10^?3, respectively, for the copolymer sample with 10 wt% of SiW₁₁KH550. The incorporation of SiW₁₁KH550 into polymer matrices is a promising approach to prepare PI films with a low dielectric constant and low dielectric loss. Copyright © 2009 John Wiley & Sons, Ltd.