Oxidative degradation of a polyimide film: I. Initial studies

High molecular weight poly-N,N′-(4,4′-diphenylether)pyromellitimide film was prepared from pyromellitic dianhydride and 4,4′-diaminodiphenylether and the oxidative degradation at 400°C was studied by weight loss measurements, infrared spectrometry and saponification experiments. The results indicated the rapid development of crosslinks between the polyimide chains.     

含羟基聚酰亚胺改性环氧胶的制备及性能研究

将3,3'-二氨基-4,4'-二羟基联苯(DADHBP)、2,2-双(3-氨基-4-羟基苯基)六氟丙烷(BAH-PFP)和3,3',4,4'-四羧酸二苯醚二酐(ODPA)、3,3',4,4'-四羧酸二苯甲酮二酐(BTDA)单体聚合,再经亚胺化得到含羟基聚酰亚胺(HPI)粉末,采用傅里叶红外光谱对其进行了表征。由HPI、烯丙基双酚A、双马来酰亚胺、2-乙基-4-甲基咪唑与N,N,N',N'-四缩水甘油基-4,4'-二氨基二苯甲烷(TGDDM)共聚反应制得胶粘剂,并对胶粘剂的热性能、力学性能及吸水性进行了研究,结果表明:该胶拉伸剪切强度为21.1 MPa,固化后吸水率为0.49%。通过凝胶化时间法计算胶粘剂的表观活化能为64.5 kJ/mol。     

Equilibrium of one-pot polymerization of polyimide

One-pot polymerization of polyimide from 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA) and 4,4′-oxydianiline (ODA) was examined. The equilibrium in the polyimide with water was examined in detail in p-chlorophenol solution during the polymerization. The equilibrium constant was expressed by log K = 1.50 + 1433 (1/T). The polymerization reaction is exothermic. The molecular weight increased with decrease of temperature. © 1996 John Wiley & Sons, Inc.     

Comparison of one-pot and two-step polymerization of polyimide from BPDA/ODA

The one-pot method polymerization of polyimide was carried out from 3,3′,4,4′-biphenyl tetracarboxylic dianhydride (BPDA) and 4,4′-oxydianiline (ODA) by the use of p-chloro-phenol as the solvent. The behavior of the polymerization was compared with that of the two-step method. The imidization reaction in the one-pot method proceeds completely in this system at even a low temperature such as 100°C. In the course of the film preparation from the solution, the embrittlement occurs when the film is prepared from polyamic acid solution, while it does not occur in the case of that from the solution of the one-pot method. A molecular weight of polyimide film is almost the same as that of precursor polyimide in the solution. In the same way, that of polyimide film is almost the same as that of precursor polyamic acid. The mechanical properties of the polyimide film prepared by the one-pot method are similar to those by the two-step method. © 1996 John Wiley & Sons, Inc.     

Novel phenylethynyl‐endcapped polyimide oligomers: Synthesis and characterization

A series of novel phenylethynyl‐endcapped polyimide oligomers were prepared by polycondensation of an aromatic diamine mixture of 1,3‐bis(4‐aminophenoxy) benzene (1,3,4‐APB) and 3,4′‐oxydianiline (3,4′‐ODA) with different aromatic dianhydrides including 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), 4,4′‐(hexafluoro isopropylidene)diphthalic anhydride (6FDA), 4,4′‐oxydiphthalic anhydride (ODPA), and 4,4′‐[2,2,2‐trifluoro‐1‐(3′,5′‐bis‐(trifluoro‐methyl)phenyl)ethylidene]diphthalic anhydride (9FDA) in the presence of 4‐phenyl‐ethynylaniline (PEA) as endcapping agent in aprotic solvent at elevated temperature. The chemical structures, thermal behavior, and melt rheological properties of the synthesized polyimide oligomers were investigated. Experimental results indicated that the fluorinated polyimide oligomers derived from 6FDA (PI‐2) and 9FDA (PI‐4) are amorphous solid resins and exhibited lower melt viscosities than those prepared from the unfluorinated aromatic dianhydrides such as BPDA and ODPA. The BPDA‐based polyimide oligomers with a molar ratio of 1,3,4‐APB/3,4′‐ODA = 50:50 (PI‐5) showed lower melt viscosity than those derived from a mixture of 1,3,4‐APB and 3,4′‐ODA with molar ratios of 75:25 and 100:0, respectively. In addition, the melt viscosity of the polyimide oligomers increased obviously with increasing of the polymer calculated molecular weights. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

The effect of molecular structure on the gas transmission rates of aromatic polyimides

A series of high-molecular weight condensation polyimides was evaluated to determine the effect of polymer molecular structure on the transmission rate of oxygen, carbon dioxide, and water vapor. The polyimide films were prepared from either 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA) or pyromellitic dianhydride (PMDA) with various diamines. The study shows that molecular structure had a strong influence on gas transmission rates with results for some films varying three orders of magnitude from that of other polyimide films. In general, the BTDA series of polyimides had overall lower gas transmission rates than the PMDA-derived series. Polymers prepared with meta-oriented diamines characteristically displayed lower gas transmission than those prepared with para-oriented diamines.     

含苯炔基侧链的聚酰亚胺树脂及其复合材料

采用联苯酐(3,4′-BPDA)与4,4′-二氨基二苯醚(4,4-ODA),3,5-二氨基-4′-苯炔基二苯甲酮(DPEB),苯炔基苯酐(PEPA)制备了不同分子质量的聚酰亚胺树脂。通过流变分析,热重分析,红外光谱,动态热力学分析及静态力学性能测试等研究了分子结构,分子质量等因素对聚酰亚胺树脂耐热性和力学性能的影响。结果表明,合成的聚酰亚胺树脂具有优异耐热性能和较高的韧性,固化后树脂的玻璃化转变温度为379℃,5%热失重温度高于550℃,并且浇注体的拉伸强度是61 MPa,断裂伸长率是6.2%.碳纤维复合材料的室温弯曲强度为1 850 MPa,层间剪切强度为84 MPa,316℃时弯曲强度为946 MPa,剪切强度为46 MPa,具有良好的高温力学保持率。     

Polyimides cross‐linked with amino group‐containing compounds

The commercially available linear polyimide Matrimid^® 9725 was crosslinked with amino groups containing both high‐molecular‐weight and low‐molecular‐weight compounds. The multi‐functional amine‐terminated hyperbranched polyimide precursor (hyperbranched polyamic acid), based on 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride and 4,4′,4″‐triaminotriphenylmethane, and its fully imidized form (amine‐terminated hyperbranched polyimide), bifunctional amine, 4,4′‐diaminodiphenylamine and trifunctional amine, 4,4′,4″‐triaminotriphenylamine, were used as the crosslinkers. Theoretically, 10% or 20% of the Matrimid imide groups was reacted with the amino groups of the crosslinking agent during the formation of the amide groups. The insoluble content (gel) in the final materials was very low at the crosslinking temperature of 80°C and was in the 55–90% range at the crosslinking temperature of 200°. The permeability coefficients of hydrogen, carbon dioxide and methane in the self‐standing, mechanically tough film (membrane) based on the combination of Matrimid and hyperbranched polyimide were approximately 30–45% higher compared with those in the membrane made of pure Matrimid at a comparable separating ability (selectivity). POLYM. ENG. SCI., 57:1367–1373, 2017. © 2017 Society of Plastics Engineers     

Preparation and Characterization of Aminopropylsilatrane Endcapped Polyimide Films

γ-Aminopropylsilatrane (APS)/γ-aminopropyltriethoxysilane (APTES) end capped polyimide films were prepared by thermal imidization method. Polyamic acid (PAA) was prepared by the reaction of 4,4′-oxydianiline (ODA) with 4,4′-oxydipthalicdianhydride (ODPA) using dimethylacetamide (DMAc) as solvent. The end group of prepared PAA was capped by different percentage of APS/APTES. The polyimide films were characterized by different advanced instrumental techniques for chemical/physical properties. APS end capped PI films show better thermal and mechanical properties and air permeability than APTES end capped polyimide films.     

Molecular weight and concentration effects on gel/sol transitions in a segmented rigid-rod polyimide solution

Gel/sol and order/disorder transitions can be observed in a segmented rigid-rod polyimide solution at different concentrations and molecular weights. This polyimide was synthesized from 3,3′,4,4′-biphenyltetracarboxylic dianhydride and 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl in refluxing 3-cresol in a one-step process. Above about 140°C, the polymers are completely soluble in 3-cresol in a concentration range up to 12(w/w)%. During cooling, the hot solutions undergo a mechanical sol/gel transition to form thermally reversible gels. In the gel state, an ordered structure develops. Both the gel/sol and order/disorder transitions are dependent upon concentration, temperature, and molecular weight, but the two transitions exhibit different kinetics. Possible mechanisms of these transitions are discussed.     

Properties of poly[N,N′-(4,4′-diphenyl ether) 4-amidophthalimide] film

A high molecular weight polyamide–imide polymer derived from the reaction of TMAC–DAPE has been prepared and its film properties have been evaluated. Poly-[N,N′-(4,4′-diphenyl ether) 4-amidophthalimide] film has an excellent combination of mechanical, electrical, and chemical properties at room temperature and at 200°C. A comparison of the film properties of this material with those of a commercial polyimide film, Teflon, FEP, Nomex paper, and Mylar films is also presented.     

Polyimide–polydimethylsiloxane copolymers for low‐dielectric‐constant and moisture‐resistance applications

Novel, randomly coupled, soluble, segmented polyimide–polydimethylsiloxane (PI–PDMS) copolymers were prepared from aminoalkyl‐terminated polydimethylsiloxane (At–PDMS), 4,4′‐oxydianiline diamine, pyromellitic dianhydride, and 4,4′‐diphenylmethane diisocyanate (MDI). When At–PDMS was introduced into the polyimide chain, the polyimide copolymers exhibited lower dielectric constants and better moisture resistance and mechanical properties. The reductions in the dielectric constant of the PI–PDMS copolymers could be attributed to the incorporation of polydimethylsiloxane (PDMS) into the polyimide chain and the nanopores in the film generated by carbon dioxide evolvement during the reaction. The lowest dielectric constant was 2.58 with 25 wt % PDMS and 5 wt % MDI. In addition, the water contact angles of the resultant copolymers increased from 51 to 109° when the contents of PDMS increased from 0 to 25 wt %. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of polyimide/oligomeric methylsilsesquioxane hybrid films

In this study, polyimide/silsesquioxane hybrid materials were synthesized from aminoalkoxysilane‐capped poly(pyromellitic dianhydride‐co‐4,4′‐oxydianiline) (PMDA‐ODA) and oligomeric methylsilsesquioxane (O‐MSSQ) precursors. The O‐MSSQ moiety was used to obtain well characterized nano‐inorganic cage and network structures in the hybrid materials. The effects of molecular structures and composition on the morphologies and properties of the prepared hybrid materials were studied. The phase separation of the prepared hybrid materials could be controlled by varying the molecular weight of the polyimide moiety, the Si? OH end group content of the O‐MSSQ or the coupling agent. Homogeneous and transparent hybrid thin films were obtained from the low molecular weight polyimide moiety with a coupling agent, 3‐aminopropyltrimethoxysilane (APrTMS). However, microphase separation occurred if the molecular weight of the polyimide moiety was enhanced or was prepared without a coupling agent, as evidenced by atomic force microscopy (AFM), field emission scanning electron microscopy (FE‐SEM), and electron spectroscopy for chemical analysis (ESCA). The high Si? OH content of the O‐MSSQ could enhance the bonding density between the organic and inorganic moiety and thus retard phase separation. The thermal and mechanical properties of the prepared hybrid materials were largely improved compared with the parent polyimide, PMDA‐ODA, and were demonstrated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and thermal‐stress analysis. The hybrid materials showed adjustable refractive index and dielectric constant by varying the O‐MSSQ content. The birefringence of the PMDA‐ODA was reduced by incorporating the O‐MSSQ moiety. This work revealed that the polyimide/O‐MSSQ hybrid materials could have potential applications as optical films or low dielectric constant materials. Copyright © 2004 Society of Chemical Industry     

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 properties of the amino‐functionalized multiple‐walled carbon nanotubes/polyimide nanocomposites

The 1,6‐hexanediamine‐functionalized multi‐walled carbon nanotubes(a‐MWNTs)/polyimide(PI) nanocomposite films were prepared through in‐situ polymerization followed by mixture casting, evaporation, and thermal imidization. To increase the compatibility of carbon nanotubes with the matrix polyimide, a‐MWNTs was used as the filler. According to the results, a‐MWNTs were homogeneously dispersed in the nanocomposite films. With the incorporation of a‐MWNTs, the mechanical properties of the resultant films were improved due to the strong chemical bonding and interfacial interaction between a‐MWNTs and 4,4′‐oxydiphthalic anhydride(ODPA)/4,4′‐Oxydianiline(ODA) polyimide matrix. The thermal stability of the a‐MWNTs/polyimide nanocomposite was also improved by the addition of a‐MWNTs. The electrical tests showed a percolation threshold at about 0.85 vol% and the electrical properties were increased sharply. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Synthesis of new sulfonated copolyimides in organic and ionic liquid media for fuel cell application

New sulfonated copolyimides containing ether, carbonyl, and bulky naphthyl group in backbone were synthesized in two reaction media: organic solvent and ionic liquid media. For this purpose a new sulfonated diamine (BANBPDS) and an unsulfonated diamine (BANBP) was prepared through reactions of 4,4′‐dichlorobenzophenone‐3,3′‐disulfonic acid, and also 4,4′‐dichlorobenzophenone with 5‐amino‐1‐sodium naphthoxide, respectively. Three series of sulfonated copolyimide with different sulfonation contents (40–80%) were prepared by reaction of the sulfonated diamine (BANBPDS) in companion with three unsulfonated diamines including BANBP, 4,4′‐oxydianiline (ODA), and 1,8‐diamino‐3,6‐dioxaoctane (DADO) with 1,4,5,8‐naphthalene tetracarboxylic dianhydride (NTDA). Two media were selected for preparation of copolyimides. Copolyimides synthesized in ionic liquid had higher inherent viscosity and higher molecular weight in comparison with similar copolyimides that were synthesized via common organic solvent method. Incorporation of flexible groups in polyimide structures increased solubility and processability of the copolyimides. After characterization of polymers with common methods, their water uptake, water stability, ion exchange capacity (IEC), thermal behavior and stability, crystallinity, and morphology were studied. The polymers showed suitable properties including high thermal stability and ion exchange capacity, which were the basic requirements for application as fuel cell membranes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

High-performance polymer films. III. Preparation and characterization

A series of polyimide and copolyimide films were prepared by film casting, drying, and thermal imidization from the respective precursor poly(amic acid) (PAA) and copoly(amic acid) solutions derived from two dianhydrides, pyromellitic dianhydride (PMDA) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and two diamines, 4,4′-oxydianiline (ODA) and a proprietary aromatic diamine (PD) as monomers. Depending on the solution's inherent viscosity value (molecular weight) and the nature of the polymer chains (derived from rigid or flexible monomers), precursor poly(amic acid) and copoly(amic acid) solution concentrations of 8–12% (w/w) were found to be suitable for the preparation of good quality polyimide/copolyimide films. The recovery of film toughness and creasability from the brittleness at the intermediate temperature of the cure cycle depended not only on the molecular weight of the precursor poly(amic acids)/copoly(amic acids) but also on their chain flexibility. The poly(amic acid) derived from both rigid dianhydride and diamine practically gave rise to a brittle film of polyimide even after curing to 360°C. The resulting polyimide and copolyimide films were compared with Du Pont's Kapton H film. The density of the films was in the range 1.39–1.42 g/cm³. The thickness of most of the films was in the range 20–30 μm. The HPF 3 film, based on PMDA–PD, appeared to be highly colored (reddish brown), and the HPF 2 film, based on BTDA–ODA, had the lightest yellow coloring among the films in this investigation, including Kapton H film. HPF 2, HPF 6, and HPF 8 films were more amorphous than the other films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 976–988, 2001     

Linear and networked blends and copolymers of polyimide

Preparation and characterization of blends and copolymers of a fluorinated polyimide with network constituents is reported. 4,4′‐Hexafluoroisopropylidene diphthalic anhydride and 4,4′‐diaminodiphenyl ether (6FDA–DDE) polyimide were used as the linear hosts and mellitic acid hexamethyl ester ‐ 4,4′‐diaminodiphenyl ether (MAHE–DDE) was employed as the network constituent for the blend and copolymer. Cast films of the polyimides were characterized by FTIR, XPS, DMA, and TGA. The multifunctional nature of MAHE facilitated crosslinking among the constituents. Both blends and copolymers showed significant improvement in the storage modulus and glass transition temperature relative to that observed for the 6FDA homopolymer. The occurrence of a single glass transition temperature for the blends suggests that they were at least partially miscible. Presence of low molecular weight species in the copolyimides, combined with steric hindrance to crosslinking, may have resulted in the existence of an optimum in the amount of the network components for improving the mechanical properties. Inclusion of network components is presented as a facile method for improving the desirable properties of polyimide. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3000–3008, 2006     

Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Water vapor sorption and transport in dense polyimide membranes

The sorption and transport of water vapor in five dense polyimide membranes were studied by thermogravimetry. The sorption isotherms of water vapor in the polyimides could be successfully interpreted by both the dual‐mode sorption model and the Guggenheim–Anderson–de Boer equation. The water vapor diffusion behavior was found to be nearly Fickian at higher water vapor activities, whereas non‐Fickian diffusion was observed at lower water activities. The phenomena could be well described by the mechanism of combined Fickian and time‐dependent diffusion. The diffusion coefficient and water vapor uptake in the polyimides were strongly dependent on the polymer molecular structure. Except for the polyimide prepared from 3,3′,4,4′‐diphenylsulfone tetracarboxylic dianhydride and 1,3‐bis(4‐aminophenoxy) benzene, the permeability of water vapor in the dense polyimide membranes predicted from the sorption measurement at 30°C corresponded well with the water vapor permeability measured at 85°C. Among the polyimides studied, pyromellitic dianhydride–4,4′‐diaminophenylsulfone (50 mol%)/4,4′‐oxydianiline (50 mol%) showed both high water sorption and diffusion and, therefore, high water vapor permeability, which for vapor permeation membranes is necessary for the separation of water vapor from gas streams. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2306–2317, 2003