Synthesis of benzophenone tetracarboxylic dianhydride and pyromellitic dianhydride incorporated biscitraconimides and their thermal polymerization

Biscitraconimides incorporated with 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA) were synthesised. Their curing behavior as well as thermal stabilities were investigated. The intermediate amic acids were prepared by the reaction of 4-amino 4′-citraconamic acid diphenyl sulphone, 4-amino 4′-citraconamic acid diphenyl ether, and 12-amino 1-citraconamic acid dodecane with BTDA and PMDA, respectively. Six amic acids formed were then imidized by cyclocondensation with acetic anhydride. The imide monomers were obtained and these were cured at 225–240°C. The thermal stabilities of the polymers so formed were investigated and compared. © 1996 John Wiley & Sons, Inc.     

Photoconductivity of a polyimide with an alicyclic diamine: Charge carrier photogeneration in the mixed layer packing arrangement

Photoconduction mechanism of a polyimide with an alicyclic diamine, PI(PMDA/DCHM), prepared from pyromellitic dianhydride (PMDA) and 4,4′-diaminodicyclohexylmethane (DCHM) was investigated. Its UV absorption spectra, fluorescence spectra, photoconductivity, and annealing effects on the photocurrent generation were measured and compared to those of CPD, N,N′-dicyclohexylpyromellitic diimide, and PI(PMDA/DMDHM) prepared from PMDA and 3,3′-dimethyl-4,4′-diaminodicyclohexylmethane (DMDHM). Photoconductivity of PI(PMDA/DCHM) depends upon the degree of molecular packing between polymer backbones. PI(PMDA/DMDHM) has no photoconductivity, probably due to a barrier to their intermolecular packing by the existence of two methyl substituents. Photoconductivity of PI(PMDA/DCHM) would be the result of the weak intermolecular interaction formed by mixed layer packing arrangement between pyromellitic moiety of one polymer backbone and N-cyclohexyl ring of another one in the ground state. Radiation absorption of this weak intermolecular interaction immediately forms a charge–transfer complex in the excited state and produces radical cation and anion charge carriers, which lead to the photoconductivity in the bulk polyimide film of PI(PMDA/DCHM). © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1433–1442, 1998     

Aromatic-Aliphatic Polyimides. I. Preparation and Properties of Polypyromellitimides from Aromatic Diamines and Oxalyl Dihydrazide

Copolyimides were prepared in two steps by ring-opening polyaddition of pyromellitic dianhydride (PMDA) with oxalyl dihydrazide (0) and an aromatic diamine; viz., diaminodiphenyl methane (M), p-phenylene diamine (P), or benzidine (B) in dimethylsulfoxide (DMSO), followed by thermal cyclodehydration. O content was restricted to 10%. Kinetics of imidization of polyamic acid samples was studied. The effect of structure and composition of copolymers on thermal properties was evaluated.     

Preparation and absorption spectrum studies of aromatic and alicyclic poly(amide acid) ammonium salts in water and DMF and in films

A series of ammonium salts of poly(amide acid)s (PAS) were prepared from various poly(amide acid)s (PAA) with tertiary amines. The solubility of poly(amide acid) ammonium salts prepared from PAA(PMDA/ODA) in water is related to the ion concentration of tertiary amines. In order to elucidate the influence of the chemical structures of poly(amide acid)s and poly(amide acid) ammonium salts on their absorption spectra, pyromellitic dianhydride (PMDA), 3,3′,4,4 ′-biphenyltetracarboxylic dianhydride (BPDA), and 3,3′,4,4 ′-benzophenonetetracarboxylic dianhydride (BTDA) were chosen to react with p-phenylenediamine (PDA) and (4,4′-diaminodicyclohexyl)methane (DCHM) to give three kinds of aromatic PAAs and three kinds of alicyclic PAAs. The corresponding PASs were prepared by the reaction of PAAs with triethanolamine (TEA). Their ultraviolet–visible (UV–vis) absorption spectra were investigated compared to those of model compounds. A transparent film without absorption above 320 nm was obtained for PAS(PMDA/DCHM). The difference in absorption spectra of PAS(PMDA/PDA) from that of PAS(PMDA/DCHM) can be related to the existence of intra- and intermolecular charge transfer (CT) for PAS(PMDA/PDA). The absorption spectra of PASs with PDA in films are red shifted compared to those of corresponding PAAs in films, while the absorption spectra of PASs in water are blue shifted compared to those of corresponding PAAs in DMF. No differences in the absorption spectra of PAAs and PASs were found in DMF/H₂O (9/1) mixed solvent. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1329–1340, 1998     

硅氧烷表面改性聚醚酯聚酰亚胺的研究

通过两种方法。即将γ-氨丙基封端的聚二甲基硅氧烷和对氨基苯甲酸酯封端的聚(四亚甲基)醚与均苯四甲酸二酐共缩聚,和将两种预制的聚酰胺酸溶液共混,合成了一组硅氧烷改性的聚醚酯聚酰亚胺材料。ESCA能谱和表面水接触角测量研究材料的表面性质发现,硅氧烷在材料表面富集,对聚醚酯聚酰亚胺材料具有显著的表面改性作用,硅氧烷改性的聚醚酯聚酰亚胺,其热稳定性能和气体透过性能有一定程度的提高,但抗张强度和介电性能有所降低。     

Partly Imidized Polyamic Acid and Its UniaxialStretched Polyimide Films

Partly imidized polyamic acid(PAA) has been used to prepare high performance polyimide films. The behaviors of two polyamic acids derived from pyromellitic dianhydride(PMDA)/4,4′-oxydianiline(ODA) and 3,3′,4,4′-biphenyltetracarboxylic diahhydride(BPDA)/paraphenylenediamine(PPD) containing dehydrating agents composed of acetic anhydride and a tertiary amine as the catalyst were investigated. The gel point was dependent on imidization degree in despite of temperature and the molar ratio of catalyst to acetic acid. Imdization content was about 35% for PMDA/ODA and about 22% for BPDA/PPD. The effect of catalyst on imidization possessed an order of triethylamine>3-methylpyridine>pyridine>isoquinoline>2-methylpyridine. The stretching of the films greatly reduced the coefficient of linear thermal expansion(CTE) either in the longitudinal direction or transversal direction. Compared to the film from polyamic acid, the partly imidized film had greater stretching ratio, so that the uniaxial stretched polyimide film from partly imidized PAA had higher tensile strength and tensile modulus, but lower elongation in the stretching direction.     

Crystalline polyimide particles generated via thermal imidization in a heterogeneous medium

Highly crystalline polyimide powders were prepared from diluted solutions of polyamic acid in N-methyl-2-pyrrolidone (NMP) which were cured at 200°C for 4 hr with a high heating rate. The chemical structures of the repetitive units were chosen to obtain rigid polymeric backbones precluding any solubility in polar aprotic solvents. Therefore the starting polyamic acids were produced by polycondensation from an equimolar ratio of the following pairs of monomers: pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (ODA); 3,3′,4,4′-biphenyl tetracarboxylic dianhydride and ODA; PMDA and p-phenylenediamine. After optimizing the reaction conditions, the resulting powders were first characterized by scanning electronic microscopy and granulometric analysis. Well-divided particles with a spherulitic shape and average particle size of 5 μm were observed. The X-ray diffraction patterns and the solid-state ¹³C nuclear magnetic resonance spectra together revealed a highly organized structure. The degree of imidization of the powder is nearly complete as demonstrated by Fourier transform infrared analysis and the inherent viscosity after dissolution in concentrated sulfuric acid is about 0.8 dl/g. © 1998 John Wiley & Sons, Ltd.     

Synthesis and properties of novel diisocyanate based optically active polyimides

A new optically active diisocyanate was prepared from the reaction of l-leucine and pyromellitic dianhydride (PMDA) and subsequent transformation of intermediate imide-containing diacid to diisocyanate via Weinstock modification of Curtius rearrangement. Solution polycondensation reaction of the prepared diisocyanate with PMDA, 3,3,4,4-benzophenonetetracarboxylic dianhydride, and hexafluoroisopropylidene 2,2-bis(phthalic anhydride) resulted in the preparation of novel optically active polyimides. The optimal conditions for polyimidations (reaction duration and temperature programming) were obtained via study of the model compound. The monomer, model compound and polymers were characterized by FTIR, ¹HNMR, mass spectroscopy and elemental analysis and their optical and physical properties were studied as well.     

均苯四甲酸酐改性花生壳粉吸附阳离子红染料的研究

以花生壳粉(PS)为生物基质,甲苯-2,4-二异氰酸酯(TDI)为交联剂,均苯四甲酸酐(PMDA)为改性剂,制备了均苯四甲酸酐改性花生壳粉(PMPS)吸附剂,并研究了PMPS对阳离子红染料吸附效果的影响因素。结果表明,在25℃,吸附时间3 h,pH值为2.0时,PMPS处理浓度为400.0 mg/mL的阳离子红溶液25 mL,最大吸附容量Q为177.2 mg/g,是未改性花生壳粉的2.2倍。改性花生壳粉吸附模式为Langmuir单分子层化学吸附。     

含磷聚酰亚胺纤维的制备及其力学与阻燃性能

采用廉价的三苯基氧膦和混酸合成了一种含磷二胺单体,二（3-氨基苯基）苯基膦氧(DAPPO)。在4,4′-二胺基二苯醚（ODA）、3,3′,4,4′-联苯四酸二酐（BPDA）和均苯四酸二酐（PMDA）聚合体系中引入该单体,制备含磷聚酰亚胺纤维。热失重分析（TGA）结果表明,聚酰亚胺纤维的热稳定性随含磷量的增加而明显提高。当n（DAPPO）：n（ODA）为7：93时,纤维的极限氧指数达到了43,说明纤维的阻燃性能显著提高。     

Preparation of novel,high‐modulus,swollen‐ or jungle‐gym‐type polyimide gels end‐crosslinked with 1,3,5‐tris(4‐aminophenyl)benzene

A novel preparation approach for high‐performance polyimide gels that are swollen or have a jungle‐gym‐type structure is proposed. A new rigid and symmetric trifunctional amine, 1,3,5‐tris(4‐aminophenyl)benzene (TAPB), was synthesized as a crosslinker. Three different kinds of amic acid oligomers derived from pyromellitic dianhydride (PMDA), 4,4′‐oxydiphthalic anhydride (ODPA), p‐phenylenediamine (PDA), and 4,4′‐oxydianiline (ODA) were end‐crosslinked with TAPB at a high temperature to make polyimide networks with different structures. Transparent polyimide gels were obtained from the ODPA–ODA/TAPB series with high compression moduli of about 1 MPa at their equilibrium swollen states in N‐methylpyrrolidone. Microscopic phase separation occurred during the gelation–imidization process when polyimide networks were generated from PMDA–PDA/TAPB and PMDA–ODA/TAPB. After these opaque polyimide networks were dried, a jungle‐gym‐like structure was obtained for the PMDA–PDA/TAPB and PMDA–ODA/TAPB series; that is, there was a high void content inside the networks (up to 70%) and little volume shrinkage. These polyimide networks did not expand but absorbed the solvent and showed moduli as high as those of solids. Therefore, using the highly rigid crosslinker TAPB combined with the flexible monomers ODPA and ODA and the rigid monomers PMDA and PDA, we prepared swollen, high‐performance polyimide gels and jungle‐gym‐type polyimide networks, respectively. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2501–2512, 2002     

Spontaneous molecular orientation of polyimides induced by thermal imidization (6). Mechanism of negative in-plane CTE generation in non-stretched polyimide films

The mechanism of negative coefficient of thermal expansion (CTE) generation for non-stretched polyimide (PI) films is proposed in this work. Negative CTE behavior was observed in some miscible binary blend films composed of a major fraction of a rod-like semi-crystalline PI derived from pyromellitic dianhydride (PMDA) with p-phenylenediamine (PDA) and flexible PIs based on 2,3,3′,4′-biphenyltetracarboxylic dianhydride (a-BPDA) whereas homo PMDA/PDA PI film shows a considerably low but a positive CTE value. The results suggest that the negative CTE generation is related to not only a considerably high extent of in-plane orientation of the PMDA/PDA chains but also to the crystallinity of the blends. The present work revealed that some other PIs, a poly(ester imide), and a polybenzoxazole system also display negative CTE and these systems also possess extremely high extents of in-plane chain orientation without exception. In addition to CTE, the morphologies were monitored as a function of imidization temperature for two PI systems, PMDA/2,2′-bis(trifluoromethyl)benzidine and PMDA/m-tolidine by wide-angle X-ray diffraction, FT-IR spectroscopy, birefringence, and film density measurements. The results suggested that the negative CTE phenomenon occurs when PI films possess very high extents of in-plane orientation and a less crystalline morphology simultaneously, thereby significant thermal expansion can be allowed to the thickness direction.     

Polyamide-imides

A novel preparation of polyamide-imides from diphenylmethane diisocyanate and trimellitic anhydride in N-methylpyrrolidone is described. Partial substitution of trimellitic anhydride with either maleopimaric acid, terephthalic acid, or by various di-anhydrides permitted a correlation of structure with solution stability and thermal properties. Heat resistance improved with increasing imide content of the polyamide-imide. Almost all solutions advanced in viscosity on storage at room temperature. The least stable solutions were those that deviated the most from 50–50 amide-imide. However, the viscosity changes depended somewhat on the type of modifying ingredient. For example, polyamide-imides modified by substitution of 10% PMDA (pyromellitic anhydride) or BPDA (benzophenone tetracarboxylic acid dianhydride) were less stable than those modified with 10% (cyclopentanetetracarboxylic acid dianhydride) CPDA or THFDA (tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride). The use of excess reagent and of monofunctional chain stopper was investigated as a means of controlling solution stability.     

The effect of chain extension on the thermal behaviour and crystallinity of reactive extruded recycled PET

Recycled poly(ethylene terephthalate) (R-PET) was chain extended with pyromellitic dianhydride (PMDA) in a commercial size twin-screw reactive extrusion system. Temperature-modulated differential scanning calorimetry (TMDSC) was used to evaluate the effect of the chain extension process on the thermal transitions and crystallinity of R-PET. Reactive extruded recycled PET (RER-PET) samples were tested based on different PMDA concentration and reactive extrusion residence times. The glass transition temperature (T _g) did not show a significant change as a function of PMDA addition or the extrusion residence time. Melting temperature (T _m) and crystallisation temperature (T _c) decreased with increasing PMDA concentration and with increasing extrusion residence time. RER-PET samples showed double melting peaks, it is believed that different melting mechanism is the reason behind this phenomenon. The crystallinity of RER-PET samples is lower than that of R-PET. RER-PET samples at constant PMDA concentration showed a decrease in crystallinity with increasing extrusion residence time. Results suggest that the reactive extrusion process is more dependent on PMDA concentration rather than reactive extrusion process residence time.The first author would like to acknowledge Advanced Engineering Center for Manufacturing (AECM) and Visy Industries for their financial support to this study.     

Influence of Steric Hindrance Between Hydrogen Atoms of Linkage Groups and Adjacent Phenyls on Properties of Polyimide

A diamine monomer 4,4′-methylenedianiline(MDA) was introduced to modify the polyimide of pyromellitic dianhydride(PMDA) and 4,4′-oxydianiline(ODA) by polycondensation. A series of polyamic acids was synthesized from MDA and ODA of different molar ratios with PMDA of sum mole of moles of MDA and ODA, and polyimide films were obtained by thermal imidization. Polyimide(PI) films were characterized by tensile testing, dynamic mechanical analysis(DMA), thermal gravimetry analysis(TGA), Fourier transform infrared spectroscopy (FTIR), wide X-ray diffraction(WAXD) and molecular simulation. With the increase of MDA content, the tensile strength and thermal decomposition temperature remained generally stable compared with those of PMDA/ODA polyimide. Unexpectedly, the glass transition temperature(T_g) and Young’s modulus increased from 388.7 ℃ and 2.37 GPa to 408.3 ℃ and 5.74 GPa, respectively. The results of WAXD and molecular simulation indicate the steric hindrance among hydrogen atoms of the linkage groups and adjacent phenyls enhanced the properties of the polyimide modified with MDA.     

Thermal behaviour of ethynyl and ethenyl terminated imide resins

A series of ethynyl and ethenyl end-capped imide resins were synthesised by the reaction of 9,9-bis(4-aminophenyl) fluorene (BAF) with pyromellitic dianhydride (PMDA)3/3′, 4,4′-benzophenone tetracarboxylic acid dianhydride (BTDA)/2,2-bis(3,4-dicarboxy phenyl) hexafluoropropane dianhydride (6F) and 3-ethynyl aniline/maleic anhydride. Structural characterisation was done by infra red and elemental analysis. Thermal characterisation was done by differential scanning calorimetry and thermogravimetric analysis. The decomposition temperatures of cured resins were above 200°C in nitrogen atmosphere. Char yield at 800°C ranged from 59–65.5%.     

Covalent molecular assembly of multilayer dendrimer ultrathin films in supercritical medium

Ultrathin films containing dendrimers are fabricated on amine- and anhydride-derivatized silicon dioxide surface through alternate layer-by-layer (LbL) assembly of pyromellitic dianhydride (PMDA) and poly(amidoamine) (PAMAM) dendrimer in supercritical carbon dioxide (SCCO2) with interlayer linkage established by covalent bonds. X-ray photoelectron and UV-visible absorption spectroscopies, atomic force microscopy (AFM), and ellipsometry were employed to study the interfacial chemistry, growth, morphology, and thickness of the assembled film. XPS analysis suggests that the PMDA/PAMAM interlayer covalent bond is established to completion, and functional surfaces for immobilization of the next layer are available after deposition of each layer. UV-visible absorption and ellipsometry revealed layer-by-layer growth of the film. The functional property film as a porous matrix was manifested in the reduction of the refractive index upon introduction of the dendrimer.     

Single vibronic level resonant Raman scattering of molecular ions in solid glass: PMDA anion and naphthalene cation

Resonant Raman spectra were obtained for the radical anion of pyromellitic dianhydride (PMDA) in MTHF glass and the radical cation of naphthalene in alkyl halide glass at 77 K by using a pulsed tunable dye laser. The intensity pattern of the single vibronic level resonant Raman resembles that of hot fluorescence when the homogeneous line width of the intermediate level is narrow. Overtones and combinations of the excited vibrational mode prevail in the spectra.     

Synthesis and thermal behaviors of 1,3-bis(4-aminophenoxy)benzene (TPER) and polyimide based on TPER and pyromellitic dianhydride

1,3-Bis(4-aminophenoxy)benzene (TPER) and poly(amic acid) based on TPER and pyromellitic dianhydride (PMDA) were synthesized. After imidization of the poly(amic acid), polyimide based on TPER and PMDA was obtained. The melting process and the specific heat capacity (C _p) of TPER were examined by DSC and microcalorimetry, respectively. The melting enthalpy, the melting entropy, and the C _p for TPER were obtained. The enthalpy change, the entropy change, and the Gibbs free energy change for TPER were obtained within 283 and 353 K. The thermal decomposition reaction mechanism of the polyimide is classified from the TG–DTG experimental data, and the thermokinetic parameters of the thermal decomposition reaction are E _a = 296.87 kJ mol^?1and log (A/s^?1) = 14.41.     

Novel polypyromellitimides and their liquid crystal aligning properties

Various aromatic poly{3,6‐bis[(4‐n‐alkyloxy)phenyloxy]‐pyromellitimide}s [poly(Ar‐C_m‐PMDA)s, m = 1, 4, 8, 12] were prepared in film form by routine two‐step condensation of 3,6‐bis[(4‐n‐alkyloxy)phenyloxy]pyromellitic dianhydrides (C_m‐PMDAs) with various aromatic diamines. After characterization of their chemical structures their solution, thermal and liquid crystal (LC)‐aligning properties in terms of pretilt angle at various rubbing densities were measured and discussed with respect to their backbone structures. All polyimide films showed excellent thermal stability and homogeneous LC alignment, but the poly(p‐phenylene‐C₁₂‐PMDA) exhibited completely homeotropic alignment while the pretilt angle values of poly(p‐phenylene‐C₈‐PMDA) varied with varying rubbing density.