Processing robustness for a phenylethynyl‐terminated polyimide composite

The processability of a phenylethynyl‐terminated imide resin matrix (PETI‐5) composite was investigated. Unidirectional prepregs were made through the coating of an N‐methylpyrrolidone solution of an amide acid oligomer (PETAA‐5/NMP) onto unsized IM7 fibers. Two batches of prepregs were used: one was made by the National Aeronautics and Space Administration in house, and the other was from an industrial source. The composite processing robustness was investigated with respect to the prepreg shelf life, the effect of B‐staging conditions, and the optimal processing window. The prepreg rheology and open hole compression (OHC) strengths were not to affected by prolonged ambient storage (i.e., up to 60 days). Rheological measurements indicated that the PETAA‐5/NMP processability was only slightly affected over a wide range of B‐stage temperatures (from 250 to 300°C). The OHC strength values were statistically indistinguishable among laminates consolidated under various B‐staging conditions. An optimal processing window was established with response surface methodology. The IM7/PETAA‐5/NMP prepreg was more sensitive to the consolidation temperature than to the pressure. A good consolidation was achievable at 371°C (700°F)/100 psi, which yielded a room‐temperature OHC strength of 62 ksi. However, the processability declined dramatically at temperatures below 350°C (662°F), as evidenced by the OHC strength values. The processability of the IM7/PETI‐5 prepreg was robust. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3212–3221, 2006     

Synthesis and characterization of bis‐triethoxysilane endcapped polyurethane/urea

A type of bistriethoxysilane endcapped polyurethane/ureas (SPU) with well‐defined structure was synthesized from bis(triethoxysiylpropyl) amine and purified prepolymers, which were obtained from the reaction of 2,4‐toluene diisocyanate (TDI) and polyoxyethylene glycol (PEG) with different molecular weight. Then, fourier transform infrared spectroscopy (FTIR), hydrogen nuclearmagnetic resonance (¹H‐NMR) and standard dibutylamine back‐titration method were used to confirm the structures of prepolymers and SPUs. Moreover, the properties of SPU were investigated by wide angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetric analyses (TGA), and percentage of water uptake. Results indicated that these polyurethanes were amorphous, and the percentage of water uptake and thermal stability of these polyurethanes went up with the increase of M _n of SPU, accompanying with the glass transition temperature (T_g) values decreased with the increase of M _n. This study provides us with a method to synthesize well‐defined end‐functionalized polyurethane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel acetylene‐terminated polyimide oligomers with excellent processability and high toughness of films

A series of acetylene‐terminated imide oligomers based on 2,3,3′,4′‐Diphenyl ether tetracarboxylic acid dianhydride (a‐ODPA), 3,4′‐Oxydianiline (3,4′‐ODA), and 3‐Ethynylaniline (3‐EA) with different molecular weights were synthesized by using acetic anhydride and triethylamine as dehydrating agent. Their main structure was confirmed by Fourier transform infrared spectroscopy (FT‐IR). Thermal curing processing was characterized by FT‐IR and differential scanning calorimetry (DSC). All the uncured imide oligomers showed excellent solubility (more than 30 wt %) in organic solvent such as N,N‐dimethylacetamide (DMAc) and N‐methyl‐2‐pyrrolidone (NMP). These imide oligomers also possessed a very low viscosity, thus provided better processing window. These oligomers were formulated into thermosetting films by thermal crosslinking of the ethynyl groups. The properties of cured films were evaluated by dynamic mechanical thermal analysis (DMA), thermogravimetric analysis (TGA), and tensile measurement. The glass transition temperature (T_g) and elongation at break of the cured films were found to be almost >260°C and >9.2%, respectively. The cured films in air resulted in higher thermal stability than those under N₂ atmosphere. Experimental results suggested that the introduction of asymmetric and flexible ether‐hinge with 3‐EA in polyimide oligomers can improve the processability of the imide oligomers and the toughness for a cured sample without sacrificing their thermal‐oxidative stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42537.     

Synthesis and characterization of fluorinated polyimide oligomers terminated with a phenylethynyl group

Novel all-aromatic phenylethynyl-terminated imide oligomers were prepared by the reaction of 4,4-oxydiphthalic anhydride (ODPA) or 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with 1,4-(4-amino-2-trifluoromethyl-phenoxy)-2-(3′-trifluoro-methylphenyl) benzene and 4-(1-phenylethynyl)1,8-naphthalic anhydride (PENA). The resulting polymers were thermally crosslinked at 370 °C. The cured polymers exhibited good solvent resistance and high thermal stability up to 540 °C under nitrogen. They also exhibited small light absorption at 1.31 and 1.55 μm. The refractive index of the polymers was in the range of 1.5515–1.5976 at 1550 nm. The surface relief depth of the phenylethyl terminated imide (PETI) oligomer films before and after curing was less than 1 nm over a range of 1 μm × 1 μm.     

Synthesis and characterization of oligosalicylaldehyde‐graft‐oligoaniline and its beginning oligomers

Conjuge bonding oligosalicylaldehyde‐graft‐oligoaniline (OSA‐graft‐OA) was synthesized from the polycondensation reaction of oligosalicylaldehyde (OSA) with oligoaniline (OA). There were various functional groups such as ? OH, ? NH and ? CH?N in the structure of the graft cooligomer. The physical properties of graft‐co‐oligomers such as melting temperature and solubility were studied: number‐average molecular weight, mass‐average molecular weight, and a polydispersity index of OA, OSA, and fractions of the graft cooligomers [(OSA‐graft‐OA)‐I] and [(OSA‐graft‐OA)‐II] were found to be 740, 780 g mol^?1,1.05; 3700, 5990 g mol^?1, 1.62; 990, 2770 g mol^?1, 2.80 and 1300, 4100 g mol^?1, 3.15, respectively. The FTIR and UV‐Vis spectra of the graft cooligomer were compared with those of beginning oligomers. The spectral analyses results showed that the OSA‐graft‐OA synthesized from the polycondensation reaction of aromatic amine with aldehyde that have long oligophenol macromolecule bonded each other with an azomethine bridge through oligophenylamine side chains. The thermal stability of the graft cooligomer and oligomers were measured by thermogravimetric analysis (TG) under an air atmosphere. According to TG analyses, the carboneous residues of the [(OSA‐graft‐OA)‐I) (soluble in ethanol) and (OSA‐graft‐OA)‐II) (soluble in toluene)] were 23 and 40%, respectively, at 1000°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 218–226, 2002     

Optimization of phthalic/maleic anhydride‐endcapped PET oligomers using response surface method

Poly(ethylene terephthalate) (PET) from off‐grades of industrial manufacturers was partially and thoroughly depolymerized in order to synthesize PET oligomers and bis(hydroxyethyl) terephthalate (BHET), respectively. Design of experiments and analysis of variance (ANOVA) were applied for optimization of samples. Effects of reaction time, volume of glycol, catalyst concentrations, and particle size of off‐grade PET were investigated. The optimal conditions to synthesize PET oligomers (3–8 repeating units) were glycol/PET molar ratio of 1, a weight ratio (catalyst to PET) of 0.5 wt%, using granule‐shape. On the other hand, a reaction time of 180 min, a weight ratio (catalyst to PET) of 0.25 wt%, and glycol/PET molar ratio of 5 were obtained as the suitable conditions of BHET production. Then, endcapped PET oligomers, as a compatibilizer for preparing PET nanocomposites, were produced via reaction between maleic anhydride/phthalic anhydride (MA/PhA) composition. The combination of reaction time of 106 min and PhA/MA molar ratio of 0.85 produced the best results based on d‐spacing and peak shift of nanocomposite samples. Moreover, the reaction of MA and BHET from glycolyzation of PET was successfully performed at 160°C and 190°C for 8 h. The optimum conditions were compared with a synthesized PET. POLYM. ENG. SCI., 54:417–429, 2014. © 2013 Society of Plastics Engineers     

Synthesis and characterization of polyimide/multi‐walled carbon nanotube nanocomposites

Polyimide/multi‐walled carbon nanotube (PI‐MWNT) nanocomposites were fabricated by an in situ polymerization process. Chemical compatibility between the PI matrix and MWNTs is achieved by pretreatment of the carbon nanotubes in a mixture of sulfuric acid and nitric acid. The dispersion of MWNTs in the PI matrix was found to be enhanced significantly after acid modification. The glass transition (T_g) and decomposition (T_d) temperature of PI‐MWNT nanocomposites were improved as the MWNT content increased from 0.5 to 15 wt%. The storage modulus of the PI/MWNT nanocomposites is nine times higher than that of pristine PI at room temperature. The tensile strength of PI doubles when 7 wt% MWNTs is added. The dielectric constant of the PI‐MWNT nanocomposites increased from 3.5 to 80 (1 kHz) as the MWNT content increased to 15 wt%. The present study demonstrates that enhanced mechanical properties can be obtained through a simple in‐situ polymerization process. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Synthesis and characterization of a positive‐working,aqueous‐base‐developable photosensitive polyimide precursor

A positive‐working, aqueous‐base‐developable photosensitive polyimide precursor based on poly(amic ester)‐bearing phenolic hydroxyl groups and a diazonaphthoquinone photosensitive compound was developed. The poly(amic ester) was prepared from a direct polymerization of 2,2′‐bis‐(3‐amino‐4‐hydroxyphenyl)hexafluoropropane and bis(n‐butyl)ester of pyromellitic acid in the presence of phenylphosphonic dichloride as an activator. Subsequently, the thermal imidization of the poly(amic ester) precursor at 300°C produced the corresponding polyimide. The inherent viscosity of the precursor polymer was 0.23 dL/g. The cyclized polyimide showed a glass‐transition temperature at 356°C and a 5% weight loss at 474°C in nitrogen. The structures of the precursor polymer and the fully cyclized polymer were characterized by Fourier transform infrared spectroscopy and ¹H‐NMR. The photosensitive polyimide precursor containing 25 wt % diazonaphthoquinone photoactive compound showed a sensitivity of 150 mJ/cm² and a contrast of 1.65 in a 3 μm film with 1.25 wt % tetramethylammonium hydroxide developer. A pattern with a resolution of 10 μm was obtained from this composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 352–358, 2002     

Synthesis and characterization of low‐dielectric photosensitive polyimide/silica hybrid materials

Photosensitive polyimide/silica hybrid materials were synthesized by reaction between 4,4′‐hexafluoroisopropylidene diphthalic anhydride (6FDA) and 4,4′‐oxydianiline. The intrachain chemical bonding and the interchain hydrogen bonding between the polyimide and silica moieties were increased by the incorporation of 2‐(dimethylamino) ethyl acrylate and 3‐aminopropyl trimetho xysilane, respectively. The photoinitiator was bis(2,4,6‐trimethyl benzoyl) phenylphosphine oxide (Irgacure‐819). The various coupling agents were utilized included tetrakis (allyloxy) silane (TAL). Most silica hybrid films showed better volume shrinkage and temperature resistance. The cooperation of octavinyl POSS, as the coupling agent, can lower dielectric constant (k) down to 2.48 but with the poorer volume shrinkage and temperature resistance than the other silica hybrid films. The addition of tetramethyl orthosilicate and 3‐methacryloxy propyltrimethoxysilane with silica content of 5.6 wt % can reduce k down to 2.26 but with worse volume shrinkage than the incorporation with TAL. The TAL hybrid film with degree of polymerization of 25 showed the best properties that optimized photolithography, dielectric constant (k = 3.81), volume shrinkage, and temperature resistance (Td5% = 378°C) with only 0.22 wt % silica content. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrosynthesis and characterization of o‐phenylenediamine oligomers

The contribution of electrochemical methods to the development of conducting polymers has been most relevant, although the electropolymerization mechanism has not yet been totally elucidated. The formation of a high‐density oligomeric region in the electrode–solution interface has been clearly established as formed by oligomers with different chain lengths. It has been confirmed that, depending on the variables governing the process (applied potential, electrolysis time, concentration, etc), it is possible to control to some extent the oligomer to be generated. In this present work, the electrosynthesis of oligomers of o‐phenylenediamine is proposed. A saturated solution of the monomer was electrolysed at 0.95 V versus SCE over 1 min, using stainless steel as the working electrode material. Under these conditions, a mixture of the dimer and tetramer, relatively easy to separate by thin layer chromatography, was deposited. The products were characterized by mass spectrometry, UV–vis spectroscopy, elemental analysis and ¹H NMR spectroscopy. This approach allows the synthesis of oligomers in a fast and simple way. In addition, the product is directly obtained on the electrode surface, hence making its separation and purification very straightforward. Copyright © 2004 Society of Chemical Industry     

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     

Synthesis and characterization of magnetorheological polyimide gels

Magnetorheological polymer gels (MRPGs) are composite fluids containing ferrous particles suspended in a polymer gel. In addition to modification of the carrier fluid, the polymer gel, which includes crosslinked copolyimide (CCPI) and solvent N‐octylpyrrolidone, also changes the surface properties of the ferrous particles, thus reducing the particle settling and improving particle redispersion. The viscosity of MRPGs can be easily adjusted by controlling the concentration of CCPI in the carrier medium. High thermally resistant CCPI is synthesized from dianhydride, diamine, diaminobenzonic acid, and crosslinker and has a high glass transition temperature because the crosslinking ratio can be controlled by the molar ratio of diamine to diaminobenzonic acid. The redispersion and rheological properties are also investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2402–2413, 2005     

Synthesis and properties of fluorene‐based polyimide adhesives

Five kinds of fluorene‐based polyimides (PIs) based on 4,4′‐oxydiphthalicanhydride (ODPA), 9,9′‐bis(4‐aminophenyl)fluorene (BAFL), and 3,4′‐diaminodiphenyl ether (3,4′‐ODA) were synthesized through two‐step method. The partially or fully imidized PI films were cast from poly(amic acid) (PAA) solution and were imidized by far‐infrared radiation at various temperatures. The degree of imidization was characterized by FT‐IR and TGA. The fully imidized PI films were characterized by DMTA, TGA, and tensile tests. The partially imidized PI films were adhered to stainless steel plates for preparing the single lap joints. Lap shear strength (LSS) at room temperature was measured to compare the adhesive strength of single lap joint. Fractured surfaces were analyzed using scanning electron microscopy (SEM). The effects of fluorene content on thermal, tensile, and adhesion properties of PIs were elaborately studied. The results showed that PI films exhibited high glass transition temperature (T_g), good thermalplasticity, and thermal stability. The LSS of PIs increased abruptly with the incorporation of fluorene groups. The LSS of PI‐50/50 was the highest, which was 22.3 MPa. The LSS of PI‐50/50 was also measured at high temperature to investigate the thermal resistance of fluorene‐based PI adhesive. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

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     

Synthesis and characterization of BDSDA/APB polyimide

A novel linear aromatic polyphenylene ethersulfideimide (BDSDA/APB) has been synthesized. Its physical, mechanical, thermal, and flow properties and its resistance to some of the more commonly used solvents were determined. The results of these property evaluations indicate this polymer system can be processed via conventional thermoplastic techniques. It has been molded, used as a resin, and cast into thin films and, accordingly, may have a wide variety of applications. Its molecular weight was varied by endcapping with phthalic anhydride. Over the M?_n range 14,000–45,000 the apparent viscosities and G_Ic values varied only slightly. However, a change in M?_n from 14,000 to 8700 resulted in a dramatic decrease in the apparent viscosity at both 250°C and 280°C. The G_Ic values for these same molecular weight materials decreased in a like manner as the M?_n decreased, indicating tradeoffs can be made between process optimization and final mechanical properties when polymer systems are developed.     

Synthesis and characterization of colorless polyimide nanocomposite films

A poly(amic acid) was prepared through the reaction of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride and 2,2′‐bis(trifluoromethyl) benzidine in N,N‐dimethylacetamide. Hybrid films were obtained from blend solutions of the precursor polymer and the organoclay dodecyltriphenylphosphonium–mica, with the organoclay content varying from 0 to 1.0 wt %. The cast films of poly(amic acid) were heat‐treated at different temperatures to create polyimide (PI) hybrid films. These PI hybrid films showed excellent optical transparency and were almost colorless. The intercalation of PI chains in the organoclay was examined with wide‐angle X‐ray diffraction and electron microscopy. In addition, the thermomechanical properties were tested with differential scanning calorimetry and thermogravimetric analysis, and the gas permeability was determined. The addition of only a small amount of the organoclay was sufficient to improve the thermal and mechanical properties of the PI, with the maximum enhancement being observed with 0.5 wt % organoclay. However, the water vapor permeability decreased with the clay loading increasing from 0 to 0.5 wt %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of self-metallizing gold-doped polyimide films

State-of-the-art methods for producing reflective polymer films for space applications involve multiple steps, and the integrity of the metal–polymer interface is less than optimal. A more efficient process was developed that consists of doping polyamic acid resins with gold additives and curing them to form self-metallizing polyimide films. Several moderately reflective, flexible metallic gold films were produced that have good thermal stability and mechanical properties, a strong metal–polymer interface, and in some cases, electrical conductivity. It was found that the polymer system, gold additive, gold concentration, and heat treatment all affect the reflectivity, flexibility, and conductivity of the resulting polyimide films by affecting the degree of metallization of the film surface. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of positive photosensitive polyimide precursors

This paper is concerned with the study of the positive photosensitive polyimide precursors, and deals with monomer synthesis, polymerization, and characterization. The polymers were prepared from diamines and diaeid chlorides whieh were derived from the reactant with biphenyltetracarboxilic dianhydride and o-nitrobenzyl alcohol. The molecular weights of the polymer were controlled by adjusting the monomer stoichiometry. The photoreaction of the polymers was confirmed from the change in IR spectra between the film exposed and unexposed to UV light from a Hg? Xe lamp. The exposed areas of the film dissolved in alkaline solution, forming the positive tones. There was a marked difference in sensitivity between the polymers having different molecular weights. Their sensitivities decrease as their molecular weights increase. Further, there was a difference in the thermal behavior. Imidization temperature was shifted to a high temperature side and thermal stabilities increased with an increase in molecular weight.     

Novel positive‐type photosensitive polyimide with low dielectric constant

A novel positive‐type photosensitive polyimide (PSPI) with a low dielectric constant was developed. The PSPI system was composed of soluble block PI (Bco‐PI) with a hydroxy group and diazonaphthoquinone as a photoreactive compound. The base Bco‐PI was prepared by a direct one‐pot polycondensation of 2,2‐bis(3‐amino‐4‐hydroxy‐phenylhexafluoropropane), 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, and cyclohexanetetracarboxylic dianhydride in the presence of a γ‐valerolactone and pyridine catalyst system using N‐methyl‐2‐pyrrolidone as the solvent. The film of Bco‐PI was colorless and transparent, both important factors for a PSPI. Photosensitive soluble block PI (Bco‐PI), containing 20 wt % ester of 2,3,4‐trihydroxybenzophenone with 1,2‐naphthoquinone‐(2)‐diazide‐5‐sulfonic acid (NT200), showed a sensitivity of 350 mJ/cm² and a contrast of 1.20 when it was exposed to UV light, followed by development with 5% tetramethylammonium hydroxide aqueous solution at room temperature. The estimated optical dielectric constants of the PIs with and without NT200 were 2.68 and 2.75, respectively. These values were significantly lower than those of conventional aromatic PIs, such as Kapton film (50EN). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 15–21, 2005     

Synthesis and characterization of oligomers containing the α‐aminoalkylphenone chromophore as oligomeric photoinitiator

An oligomeric photoinitiator containing α‐aminoalkylphenone photoactive chromophore in the main chain was prepared from diphenyl ether, α‐chloroisobutyryl chloride, and piperazine through acylation, bromination, epoxidation, and polycondensation. The obtained oligomeric photoinitiator was characterized by GPC, TGA, traditional DSC, FTIR, NMR, UV–vis absorption, and fluorescence spectroscopy. The number‐average molecular weight (M_n) of the oligomeric photoinitiator was determined to be 2000–4000. The excitation and emission wavelengths of the fluorescence spectra were 376 and 473 nm, respectively. The thermal stability of the oligomer was found to be perfect with a decomposition temperature greater than 300°C. All the spectroscopic and thermal analyses clearly confirmed the consistence of property and structure. In a comparative photo‐DSC investigation, the oligomeric photoinitiator showed high photoinitiating efficiency while using 1,6‐hexanediol diacrylate as monomer. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3417–3424, 2006