γ‐Butyrolactone‐processable high‐modulus poly(ester imide)s

γ‐Butyrolactone (GBL)‐processable high modulus heat‐resistant materials were developed in this work. The polyaddition of an ester‐containing tetracarboxylic dianhydride, i.e. hydroquinone bis(trimellitate anhydride) (TAHQ), and 2,2′‐bis(trifluoromethyl)benzidine (TFMB) in GBL resulted in gelation in the initial reaction stage. The incorporation of a methyl group to TAHQ (M‐TAHQ) allowed polymerization with TFMB in GBL and led to a homogeneous poly(ester imide) (PEsI) precursor solution with a short pot life of 3 days, whereas a simple copolymerization approach using bulky/flexible comonomers to TAHQ/TFMB was less effective. PEsI precursors (PEsAAs) were prepared from TFMB, M‐TAHQ and a minor fraction of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) or a fluorene‐containing tetracarboxylic dianhydride. These PEsAA systems showed drastically improved GBL solution stability. In particular, the M‐TAHQ(80);6FDA(20)/TFMB copolymer system provided a PEsAA film with a very high light transmittance at 365 nm (>70%). A photosensitive film composed of this matrix resin and diazonaphthoquinone provided a clear positive‐tone pattern by development in a 2.38 wt% tetramethylammonium hydroxide aqueous solution at room temperature with a high dissolution contrast. The thermally cured PEsI film achieved a very high tensile modulus (>5 GPa) as the present target with other desirable properties, i.e. sufficient film flexibility, a relatively low coefficient of thermal expansion, a high T_g and low water absorption. The present materials can be promising candidates as novel buffer coat films in semiconductor applications. Copyright © 2011 Society of Chemical Industry     

Thermally stable and organosoluble cardo binaphthylene based poly(amide imide)s and poly(ester imide)s

A new imide‐containing dicarboxylic acid based on a twisted binaphthylene unit, 2,2′‐bis(N‐trimellitoyl)‐1,1′‐binaphthyl (1), was synthesized from 1,1′‐binaphthyl‐2,2′‐diamine and trimellitic anhydride in glacial acetic acid. The structure of compound 1 was fully characterized with spectroscopic methods and elemental analysis. Series of thermally stable and organosoluble poly(amide imide)s (4a–4d) and poly(ester imide)s (5a–5d) with similar backbones were prepared by the triphenyl phosphite and diphenylchlorophosphate activated direct polycondensation of diimide dicarboxylic acid 1 with various aromatic diamines and diols, respectively. With due attention to the structural similarity of the resulting poly(amide imide)s and poly(ester imide)s, most of the differences between these two block copolyimides could be easily attributed to the presence of alternate amide or ester linkages accompanied by imide groups in the polymer backbone. The ultraviolet maximum wavelength values of the yellowish polymers were determined from their ultraviolet spectra. The crystallinity of these copolyimides was estimated by means of wide‐angle X‐ray diffraction, and the resultant polymers exhibited a nearly amorphous nature, except for the polymers derived from benzidine and 4,4′‐binaphthol. The poly(amide imide)s exhibited excellent solubility in a variety of highly polar aprotic solvents, whereas the poly(ester imide)s showed good solubility in less polar solvents. According to differential scanning calorimetry analyses, polymers 4a–4d and 5a–5d had glass‐transition temperatures between 331 and 357°C and between 318 and 342°C, respectively. The thermal behaviors of the obtained polymers were characterized by thermogravimetric analysis, and the 10% weight loss temperatures of the poly(amide imide)s and poly(ester imide)s were between 579 and 604°C and between 566 and 577°C in nitrogen, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3203–3211, 2006     

Organosoluble,low‐dielectric‐constant fluorinated polyimides based on 2,6‐bis(4‐amino‐2‐trifluoromethylphenoxy)naphthalene

A novel fluorinated bis(ether amine) monomer, 2,6‐bis(4‐amino‐2‐trifluoromethylphenoxy) naphthalene, was prepared through the nucleophilic aromatic substitution reaction of 2‐chloro‐5‐nitrobenzotrifluoride and 2,6‐dihydroxynaphthalene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of novel trifluoromethylated polyimides were synthesized from the diamine with various commercially available aromatic tetracarboxylic dianhydrides using a two‐stage process with thermal imidization of poly(amic acid) films. Most of the resulting polyimides were highly soluble in a variety of organic solvents and could afford transparent and tough films via solution casting. These polyimides exhibited moderately high glass transition temperatures (T_gs) of 249–311 °C, high thermal stability and good mechanical properties. Low moisture (0.19–0.85 %), low dielectric constants (2.49–3.59 at 10 kHz), and low color intensity were also observed. For a comparative study, a series of analogous polyimides based on 2,6‐bis(4‐aminophenoxy)naphthalene were also prepared and characterized. Copyright © 2005 Society of Chemical Industry     

Synthesis and properties of poly(ether imide)s derived from 2,5‐bis(3,4‐dicarboxyphenoxy)biphenyl dianhydride and aromatic ether–diamines

A series of poly(ether imide)s (PEIs) with light colors and good mechanical properties were synthesized from 2,5‐bis(3,4‐dicarboxyphenoxy)biphenyl dianhydride and various aromatic ether–diamines via a conventional two‐step polymerization technique that included ring‐opening polyaddition at room temperature to poly(amic acid)s (PAAs) followed by thermal imidization. The precursor PAAs had inherent viscosities ranging from 0.71 to 1.19 dL/g and were solution‐cast and thermally cyclodehydrated to flexible and tough PEI films. All of the PEI films were essentially colorless, with ultraviolet–visible absorption cutoff wavelengths between 377 and 385 nm and yellowness index values ranging from 10.5 to 19.9. These PEIs showed high thermal stabilities with glass‐transition temperatures of 206–262°C and decomposition temperatures (at 10% weight loss) higher than 478°C. They also showed low dielectric constants of 3.39–3.72 (at 1 MHz) and low water absorptions below 0.85 wt %. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polyimides 7: Synthesis,characterization, and properties of novel soluble semifluorinated poly(ether imide)s

Three novel diamine monomers ( VI , VII , and VIII ) were synthesized. These diamine monomers lead to a number of semifluorinated poly(ether imide)s when reacted with different commercially available dianhydrides like pyromellitic dianhydride (PMDA), benzophenone tetracarboxylic acid dianhydride (BTDA), 2,2‐bis (3,4‐dicarboxyphenyl) hexafluoropropene (6FDA), and oxydiphthalic dianhydride (ODA) by thermal imidization route. Elemental analyses, IR and NMR techniques were used to characterize the monomers and polymers. The resulting polymers exhibited weight average molar masses up to 1.78 × 10⁵ g mol^?1 in GPC with respect to polystyrene standard and have very good solubility in several organic solvents such as NMP, DMF, DMAC, DMSO, chloroform, and THF. Very good solubility of these polymers in CDCl₃ enables their complete characterization by proton as well as ¹³C‐NMR techniques. The polymers showed very high thermal stability with decomposition temperature (5% weight loss) up to 511°C in air and high glass transition temperature up to 311°C depending upon the exact repeating unit structure. The polymer films showed high modulus (up to 2.9 GPa) as was evaluated by DMA. The polymers also showed very low water absorption (0.16%), low dielectric constant (2.35 at 1MHz) and very good optical transmission. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3025–3044, 2007     

Synthesis and properties of soluble fluorinated poly(ether imide)s with different pendant groups

Two types of new fluorinated diamine monomer, [1,4-(4-amino-2-trifluoromethyl-phenoxy)-2-(3′-trifluoromethylphenyl) benzene (III)] and [1,4-(4-amino-2-trifluoromethyl-phenoxy)-2-(3′-methylphenyl) benzene (IV)] were synthesized and polymerized with aromatic dianhydrides. A series of soluble poly(ether imide)s (PEIs) were prepared from the diamines and dianhydrides by two-step chemical imidization methods. Experimental results indicated that all the PEIs had glass transition temperature between 230 °C and 247 °C, the temperature at 5% weight loss between 527 °C and 598 °C under nitrogen. The membranes hand tensile strengths in the range of 74-101 MPa, tensile modulus in the range of 1.9-2.6 GPa, and elongation at break from 20 to 28%. The cast membranes also exhibited high optical transparency, with a UV-vis absorption edge of 354-406 nm. Moreover, these PEIs membranes possessed low dielectric constants of 2.63-3.20 (at 1 MHz) and low water uptakes (<0.75 wt%).     

Poly(ether imide)s containing cyano substituents and thin films made from them

A series of poly(ether imide)s containing functional cyano groups has been prepared by polycondensation reaction of 2,6‐bis(m‐aminophenoxy)benzonitrile with different bis(ether dianhydride)s, such as 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]isopropane dianhydride, 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)‐phenyl]hexafluoroisopropane dianhydride, 1,1‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]cyclohexane dianhydride, and 3,3‐bis[4‐(3,4‐dicarboxyphenoxy) phenyl]phthalide dianhydride. The polymers were soluble in polar aprotic solvents and even in less polar solvents and were processed into thin films by casting their solutions. The properties of the polymers, particularly the crosslinking of macromolecular chains through cyano groups, were studied by using dynamic mechanical analysis (DMA), thermal stability, glass transition, and solubility measurements. Also, the molecular relaxations were evidenced by DMA and dielectric spectroscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Secondary dopants modified PEDOT‐sulfonated poly(imide)s for high‐temperature range application

Poly(3,4‐ethylenedioxythiophene) (PEDOT) was polymerized using sulfonated poly(amic acid)s templates (SPAA1 and SPAA2) by batch operation. The new method was invented to enhance conductivities (ca. 100 ‐ to 2000‐fold) and with less reaction time from previous work (7 days vs. 3 days). Moreover, to increase the conductivity, many dopants were introduced as secondary doping compared with DMF, D ‐sorbitol, and surfynol that were previously used. After annealing at 180°C for 10 min, PEDOT‐SPAA1 and PEDOT‐SPAA2 doped with benzo‐1,4‐dioxan and quinoxaline showed the increase in conductivity by higher percentage than any other systems, especially doped with D ‐sorbitol and surfynol. These showed the promising tendency to develop the annealing activated superior conductivity materials after further modifying the conducting film forming processes. However, PEDOT‐SPAAs doped with benzo‐1,4‐dioxan, imidazole and quinoxaline via annealed at 180°C for 10 min were found to be more conductive than doped with DMF, but still lower conductive than doped with D ‐sorbitol and surfynol. In terms of particle size, the stable aqueous dispersions of conducting polymers prepared were comparable to polystyrene sulfonate template. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and properties of aromatic polyimide,poly(benzoxazole imide), and poly(benzoxazole amide imide)

Two series of heterocyclic aromatic polymers were synthesized from 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthaltic anhydride) and 2,2′‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride by two‐step method. The inherent viscosities were in the range of 24–45 cm³/g. The effects of the rigid benzoxazole group in the backbone of copolymer on the thermal, mechanical, and physical properties were investigated. These polymers exhibit good thermal stability. The temperatures of 5% weight loss (T₅) of these polymers are in the range of 403–530°C in air and 425–539°C in nitrogen. The chard yields of these polymers are in the range of 15–24% in air and 54–61% in nitrogen. These polymers also have high glass‐transition temperatures and a low coefficient of thermal expansion and good mechanical properties. The poly(benzoxazol imide) has a higher tensile strength and modulus than those of neat polyimide. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Organosoluble,low‐dielectric‐constant fluorinated polyimides based on 9,9‐bis[4‐(4‐amino‐2‐trifluoromethyl‐ phenoxy)phenyl]xanthene

A new trifluoromethylated bis(ether amine) monomer, 9,9‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]xanthene (BATFPX), was prepared through the nucleophilic aromatic substitution reaction of 2‐chloro‐5‐nitrobenzotrifluoride and 9,9‐bis(4‐hydroxyphenyl)xanthene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine and Pd/C in ethanol. A series of novel fluorinated polyimides were synthesized from BATFPX with various commercially available aromatic tetracarboxylic dianhydrides by one‐step polycondensation in m‐cresol. The resulting polyimides were readily soluble in many organic solvents such as N,N‐dimethylacetamide and tetrahydrofuran, and afforded transparent, flexible and strong films with low moisture absorption (0.28–0.51%), low dielectric constant (2.85–3.26 at 1 MHz) and good optical transparency with UV‐visible absorption cut‐off wavelengths at 352–410 nm. All the polyimides were amorphous and exhibited high thermal stability, with glass transition temperatures of 282–330 °C, 5% weight loss temperatures above 520 °C in nitrogen or air and char yields higher than 55% at 800 °C in nitrogen. Also, these polyimides had good mechanical properties with tensile strengths of 93–118 MPa, elongations at break of 9–16% and initial moduli of 2.07–2.58 GPa. Copyright © 2011 Society of Chemical Industry     

Synthesis and properties of fluorinated polyimides from 1,1‐bis(4‐amino‐3,5‐dimethylphenyl)‐1‐(3,4,5‐trifluorophenyl)‐2,2,2‐trifluoroethane and various aromatic dianhydrides

A novel aromatic diamine, 1,1‐bis(4‐amino‐3,5‐dimethylphenyl)‐1‐(3,4,5‐trifluorophenyl)‐2,2,2‐trifluoroethane, containing a pendant polyfluorinated phenyl group, a trifluoromethyl group, and methyl groups ortho‐substituted to the amino groups in the structure was synthesized and characterized. The diamine was polymerized with several aromatic dianhydrides, including 3,3′,4,4′‐biphenyltetracarboxylic dianhydride, 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride, 4,4′‐oxydiphthalic anhydride, and 4,4′‐hexafluoroisopropylidene diphthalic anhydride, via a high‐temperature one‐step procedure to afford four polyimides (PIs) with inherent viscosities of 0.47–0.70 dL/g. The PIs exhibited excellent solubilities in a variety of organic solvents. They were soluble not only in polar aprotic solvents but in many common solvents, such as cyclopentanone, tetrahydrofuran, and even toluene at room temperature. The tough and flexible PI films cast from the PI solutions exhibited good thermal stabilities and acceptable tensile properties. The glass‐transition temperatures were in the range 312–365°C, and the 5% weight loss temperatures were all higher than 480°C in nitrogen. The films had tensile strengths in the range 76–99 MPa, tensile moduli of 2.2–2.8 GPa, and elongations at break of 5–8%. In addition, the PI films exhibited excellent transparency in the visible light region with cutoff wavelength as low as 302 nm and transmittance higher than 88% at the wavelength of 450 nm. The PI films showed low dielectric constants ranging from 2.50–2.68 and low moisture absorptions of less than 0.56%. The good combined properties of the PIs mainly resulted from the synergic effects of the different substituents. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel thermally stable poly(ether imide ester)s from 2,6‐bis (4‐aminophenoxy) pyridine

2,6‐Bis (4‐aminophenoxy) pyridine was prepared via reaction of 4‐aminophenol with 2,6‐dichloropyridine in the presence of potassium carbonate in N‐methyl‐2‐pyrrolidone (NMP). This pyridine‐based ether diamine was reacted with two moles of trimellitic anhydride to synthesize related diimide‐diacid (DIDA). A high temperature solution polycondensation reaction of DIDA with different diols in the presence of triethylamine hydrochloride in dichlorobenzene resulted in different poly(ether imide ester)s. The monomer and polymers were fully characterized, and the physical and thermal properties of the polymers were studied. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 570–576, 2005     

Preparation of novel pyridine‐based,thermally stable poly(ether imide)s

Two aromatic, pyridine‐based ether diamines were prepared by the nucleophilic aromatic substitution reaction of 4‐aminophenol and 5‐amino‐1‐naphthol with 2,6‐dichloropyridine in N‐methyl‐2‐pyrrolidone as a solvent. Polycondensation reactions of the obtained diamines with pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and hexafluoroisopropylidene diphthalic anhydride resulted in six pyridine‐based, thermally stable poly(ether imide)s. The prepared monomers and polymers were characterized by common spectroscopic methods. The physical and thermal properties of the polymers, including the thermal behavior, thermal stability, solubility, and solution viscosity, were studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 22–26, 2004     

Oligomeric poly(ether‐imide)s bearing ortho trifluoromethyl groups: Solubility,thermal studies,and optical properties

In the development of processable high‐temperature materials, six new aromatic poly(imide)s based on diamines containing ortho trifluoromethyl groups, ether linkages and R,R‐methylenes moieties (R = Me or Ph) and previously reported dianhydrides have been synthesized vía polycondensation reactions. All polymers were obtained with good yields, were soluble in a variety of polar aprotic solvents, and exhibited inherent viscosity (η_inh) values between 0.15 and 0.20 dL g^?1, which is indicative of low molecular‐weight species. Preliminary studies of their physical properties were carried out. The new materials were transparent in the visible region and they exhibited thermal decomposition temperatures ranging from 475 to 545 °C and glass‐transition temperatures varying from 288 to 304 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46613.     

Synthesis,characterization, and gas transport properties of new semifluorinated poly(ether imide)s containing cardo moiety

A series of new semifluorinated poly(ether imide)s (PEI)s was synthesized from a diamine monomer, 9,9‐bis ‐[3‐phenyl‐4‐{2′‐trifluoromethyl‐4′‐(4′′‐aminophenyl)phenoxy} phenyl]fluorene on reaction with three different aromatic dianhydrides namely, 4,4′‐(4,4′‐isopropylidenediphenoxy)bis (phthalic anhydride), 4,4'‐(hexafluoro‐isopropylidene)diphthalic anhydride, and 4,4'‐oxydiphthalic anhydride. The PEIs were well characterized by elemental analysis, spectroscopic, thermal, mechanical, electrical, and optical techniques. The synthesized PEIs showed high glass transition temperature (T_g up to 288 °C) and high thermal stability (T_{d ,10} up to 521 °C under synthetic air), high tensile strength, up to 76 MPa and low dielectric constant (?) (2.35–2.61 at 1 MHz). The membranes prepared from these polymers were studied for their gas permeability for four different gases CO₂, O₂, N₂, and CH₄. The PEI membranes showed high gas permeability (P _CO2 up to 70.3 and P _O2 up to 16.7 Barrer) and high permselectivity (P _CO2/P _CH4 up to 73.6 and P _O2/P _N2 up to 13.4); for the O₂/N₂ gas pair the PEIs surpassed the present upper boundary limit of 2008 drawn by Robeson. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45213.     

Light‐colored fluorinated polyimides based on 2,5‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl and various aromatic dianhydrides

A novel trifluoromethyl‐containing aromatic diamine monomer, 2,5‐bis (4‐amino‐2‐trifluoromethylphenoxy)biphenyl (2), was prepared through the nucleophilic substitution reaction of 2‐chloro‐5‐nitrobenzotrifluoride and phenylhydroquinone in the presence of potassium carbonate to yield the intermediate dinitro compound (1), followed by catalytic reduction with hydrazine and Pd/C. A series of fluorinated polyimides (code 5a–f) were synthesized from diamine (2) with six commercially available aromatic dianhydrides using a standard two‐stage process with thermal or chemical imidization of poly(amic acid). Most of fluorinated polyimides showed good solubility at a concentration of 5–10 wt % and even in pyridine and dioxane. For improving solubility of 5c, copolyimides (5c/a–f) were also prepared from 2 and a pair of dianhydrides (3c/a–f), which were mixed in the molar ratio 1:1. All the polyimide films had a tensile strength in the range from 73 to 112 MPa, an elongation at break within a range of 9–23%, and an initial modulus in the range of 1.6–2.2 GPa. These polyimides exhibited glass transition temperatures of 220–267°C and showed no significant decomposition below 500°C under either nitrogen or air atmosphere. In comparison with the analogous nonfluorinated polyimides based on 2,5‐bis (4‐aminophenoxy) biphenyl (2′), the fluorinated polyimides showed better solubility as well as reduced color intensity, lower dielectric constant, and moisture absorption. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4101–4110, 2006     

Synthesis,characterization, and comparison of properties of novel fluorinated poly(imide siloxane) copolymers

Four new poly(imide siloxane) copolymers were prepared by a one‐pot solution imidization method at a reaction temperature of 180°C in ortho‐dichlorobenzene as a solvent. The polymers were made through the reaction of o‐diphthaleic anhydride with four different diamines—4,4′‐bis(p‐aminophenoxy‐3,3″‐trifluoromethyl) terphenyl, 4,4′‐bis(3″‐trifluoromethyl‐p‐aminobiphenyl ether)biphenyl, 2,6‐bis(3′‐trifluoromethyl‐p‐aminobiphenyl ether)pyridine, and 2,5‐bis(3′‐trifluoromethyl‐p‐aminobiphenylether)thiopene—and aminopropyl‐terminated poly dimethylsiloxane as a comonomer. The polymers were named 1a , 1b , 1c , and 1d , respectively. The synthesized polymers showed good solubility in different organic solvents. The resulting polymers were well characterized with gel permeation chromatography, IR, and NMR techniques. ¹H‐NMR indicated that the siloxane loading was about 36%, although 40 wt % was attempted. ²⁹Si‐NMR confirmed that the low siloxane incorporation was due to a disproportionation reaction of the siloxane chain that resulted in a lowering of the siloxane block length. The films of these polymers showed low water absorption of 0.02% and a low dielectric constant of 2.38 at 1 MHz. These polyimides showed good thermal stability with decomposition temperatures (5% weight loss) up to 460°C in nitrogen. Transparent, thin films of these poly(imide siloxane)s exhibited tensile strengths up to 30 MPa and elongations at break up to 103%, which depended on the structure of the repeating unit. The rheological properties showed ease of processability for these polymers with no change in the melt viscosity with the temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of soluble poly(ether imide)s containing fluorenyl cardo groups

Two series of poly(ether imide)s (PEIs) containing fluorenyl cardo groups in the main chains were synthesized, which are derived from the polycondensation of 9,9′‐bis(4‐aminophenoxyphenyl)fluorene (BAOFL) or 9,9′‐bis(3‐trifluoromethyl,4‐aminophenoxyphenyl)fluorene (6F‐BAOFL) with four kinds of dianhydrides (3,3′,4,4′‐biphenyltetracarboxylic dianhydride, 4,4′‐oxydiphthalicanhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and bisphenol‐A dianhydride), respectively. The PEI films and PEI powder were prepared by thermal and chemical imidization, respectively. The PEIs were characterized by FTIR, ¹H‐NMR, differential scanning calorimetry, thermogravimetric analysis, and UV–vis were performed on inherent viscosity, solubility, and tensile tests. The effects of fluorenyl cardo groups and ether linkages on the solubility, tensile properties, thermal stability, and optical properties were investigated in detail. It was found that the PEIs had good solubility in common organic solvents and good optical transparency in visible light region. In addition, the PEI films exhibited excellent tensile and thermal properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

High‐performance copoly(benzimidazole‐benzoxazole‐imide) fibers: Fabrication,structure, and properties

Novel high‐performance copolyimide (co‐PI) fibers containing benzimidazole and benzoxazole ring in the main chain were prepared by a two‐step spinning via the poly(amic acid)s. Effects of the incorporated benzimidazole and benzoxazole units on the micro‐structure and properties of co‐PI fibers were investigated. Fourier transform infrared (FTIR) results indicated that hydrogen bonding is formed in the co‐PI fibers. The co‐PI fibers exhibited discernible crystallization peaks at 14°～15° and 23°～26° (2θ), showing crystalline‐like structure. Moreover, the packing type of benzimidazole‐imide units determined the macromolecules packing of co‐PIs. It was amazedly found that the co‐PI fibers exhibited higher tensile strength and initial modulus than those of corresponding homo‐PI fibers, reaching tensile strength of 2.2–2.6 GPa, initial modulus of 99.1–113.2 GPa. The results of dynamic mechanical analysis (DMA) indicated co‐PI2 fiber had a positive T_g deviation due to the presence of strong intermolecular hydrogen bonding between benzimidazole‐imide and benzoxazole‐imide units, which maybe lead to the effective stress transfer between benzimidazole‐imide units and benzoxazole‐imide units. In addition, the obtained PI fibers exhibited excellent thermal properties with the 10% weight loss temperatures under N₂ in the range of 574–585°C. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42001.     

Synthesis and characterization of novel soluble pyridine‐containing polyimides based on 4‐phenyl‐2,6‐bis[4‐(4‐aminophenoxy)phenyl]‐pyridine and various aromatic dianhydrides

A new kind of pyridine‐containing aromatic diamine monomer, 4‐phenyl‐2,6‐bis[4‐(4‐aminophenoxy)phenyl]‐pyridine (PAPP), was successfully synthesized by a modified chichibabin reaction of benzaldehyde and a substituted acetophenone, 4‐(4‐nitrophenoxy)‐acetophenone (NPAP), followed by a reduction of the resulting dinitro compound 4‐phenyl‐2,6‐bis[4‐(4‐nitrophenoxy)phenyl]‐pyridine (PNPP) with Pd/C and hydrazine monohydrate. The aromatic diamine was employed to synthesize a series of new pyridine‐containing polyimides by polycondensation with various aromatic dianhydrides in N‐methy‐2‐pyrrolidone (NMP) via the conventional two‐step method, i.e., ring‐opening polycondensation forming the poly (amic acid)s and further thermal or chemical imidization forming polyimides. The inherent viscosities of the resulting polyimides were in the range of 0.79–1.13 dL/g, and most of them were soluble in common organic solvents such as N,N‐dimethylacetamide (DMAc), NMP, and tetrahydrofuran (THF), etc. Meanwhile, strong and flexible polyimide films were obtained, which had good thermal stability, with the glass transition temperatures (T_g) of 268–338°C and the temperature at 5% weight loss of 521–548°C in air atmosphere, as well as outstanding mechanical properties with tensile strengths of 89.2–112.1 MPa and elongations at break of 9.5–15.4%. The polyimides also were found to possess low dielectric constants ranging from 2.53 to 3.11. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 212–219, 2007