Colorless polyimides with low coefficient of thermal expansion derived from alkyl‐substituted cyclobutanetetracarboxylic dianhydrides

Alkyl‐substituted cyclobutanetetracarboxylic dianhydrides (CBDAs) were synthesized by photo‐dimerization of alkyl‐substituted maleic anhydrides to obtain novel colorless polyimides (PIs). Dimethyl‐substituted CBDA (DM‐CBDA) showed much higher polymerizability with various diamines than conventional cycloaliphatic tetracarboxylic dianhydrides and led to high molecular weights of PI precursors. Polyaddition of non‐substituted CBDA and trans‐1,4‐cyclohexanediamine (t‐CHDA) was completely inhibited by salt formation in the initial reaction stage. The use of DM‐CBDA allowed the formation of a homogeneous/viscous PI precursor solution by overcoming the salt formation problem. The prominent substituent effect probably reflects how the methyl substituents of DM‐CBDA contributed to increasing the salt solubility. Some of the thermally imidized DM‐CBDA‐based systems simultaneously possessed non‐coloration, low coefficient of thermal expansion (CTE), very high T_g exceeding 300 °C and very low dielectric constant. Copolymerization was very effective for improving the solubility of DM‐CBDA‐based PIs. The copolyimide cast films prepared via chemical imidization displayed a further decreased CTE without sacrificing other target properties, suggesting that the present materials can be useful as plastic substrates in display devices. The mechanism of self‐chain orientation behavior during solution casting is also discussed. A potential application of the copolyimide systems as optical compensation film materials in liquid crystal displays is proposed. © 2013 Society of Chemical Industry .     

Colorless polyimides derived from 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride,self-orientation behavior during solution casting,and their optoelectronic applications

A novel cycloaliphatic monomer for polyimides (PI), 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride (H′-PMDA) is proposed in this work. H′-PMDA shows high polymerizability with various diamines in contrast to its isomer, i.e., conventional hydrogenated pyromellitic dianhydride (H-PMDA) and leads to highly flexible and colorless PI films with very high T_g's. In particular, the combinations with rigid structures of diamines give rise to PIs with significantly decreased coefficients of thermal expansion (CTE) owing to high extents of in-plane chain orientation induced by thermal imidization, whereas the H-PMDA-based counterparts do not. The decreased CTE reflects structural rigidity/linearity of the H′-PMDA-based diimide units as supported by liquid crystallinity observed in the corresponding model compound. Solution casting of a chemically imidized PI derived from H′-PMDA and 2,2′-bis(trifluoromethyl)benzidine (TFMB) results in a lower CTE than that of the thermally imidized counterpart, suggesting the presence of a self-orientation phenomenon during solvent evaporation. The mechanism is proposed in this work. H′-PMDA/TFMB and its copolymer systems can be useful as plastic substrates in image display devices and/or novel coating-type optical compensation films.     

Optically transparent aromatic poly(ester imide)s with low coefficients of thermal expansion. 2: Effect of the introduction of alkyl‐substituted p‐biphenylene units

A series of ester‐linked tetracarboxylic dianhydrides (TA‐X) were synthesized from trimellitic anhydride chloride and 4,4′‐biphenol analogs containing different numbers and positions of methyl substituents. Aromatic poly(ester imide)s (PEsIs) were polymerized from TA‐Xs and 2,2′‐bis(trifluoromethyl)benzidine to investigate the film properties systematically. A significant substituent effect on the target properties (T_g, optical transparency, the linear coefficient of thermal expansion (CTE) and ductility) was observed. A PEsI containing 2,2′,3,3′,5,5′‐hexamethyl‐substituted p‐biphenylene units was chemically imidized in a homogeneous state. It was highly soluble at room temperature, even in less hygroscopic non‐amide solvents such as cyclopentanone (CPN), and provided a stable CPN solution with a high solid content. The CPN‐cast PEsI film was almost colorless as suggested from the rather low yellowness index (3.2), high light transmittance at 400 nm (71.5%) and very low haze (1.15%). This PEsI film also had a high T_g (294 °C, determined by thermomechanical analysis) in addition to a low CTE (21.7 ppm K^?1), moderate film ductility and very low water uptake. A structural modification of the PEsI by copolymerization with a tetracarboxylic dianhydride with a rigid/linear structure was effective in further reducing the CTE while maintaining the other excellent target properties. Thus, some of the PEsIs developed in this work are promising candidates as novel plastic substrates for use in image display devices. © 2017 Society of Chemical Industry     

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     

Effects of thermal imidization on mechanical properties of poly(amide‐co‐imide)/multiwalled carbon nanotube composite films

In this study, experimental and numerical studies were performed to investigate the relationship among the functionalization method, weight fraction of MWCNTs, thermal imidization cycle, and mechanical properties of various PAI/MWCNT composite films. Poly(amide‐co‐imide)/multiwalled carbon nanotube composite films were prepared by solution mixing and film casting. The effects of chemical functionalization and weight fraction of multiwalled carbon nanotubes on thermal imidization and mechanical properties were investigated through experimental and numerical studies. The time needed to achieve sufficient thermal imidization was reduced with increasing multiwalled carbon nanotube content when compared with that of a pure poly(amide‐co‐imide) film because multiwalled carbon nanotubes have a higher thermal conductivity than pure poly(amide‐co‐imide) resin. Mechanical properties of pure poly(amide‐co‐imide) and poly(amide‐co‐imide)/multiwalled carbon nanotube composite films were increased with increasing imidization time and were improved significantly in the case of the composite film filled with hydrogen peroxide treated multiwalled carbon nanotubes. Both the tensile strength and strain to failure of the multiwalled carbon nanotube filled poly(amide‐co‐imide) film were increased substantially because multiwalled carbon nanotube dispersion was improved and covalent bonding was formed between multiwalled carbon nanotubes and poly(amide‐co‐imide) molecules. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Mechanisms of ultralow and anisotropic thermal expansion in cordierite Mg2Al4Si5O18: Insight from phonon behaviors

Materials with negative or ultralow thermal expansion are of crucial importance for technological applications since they make it possible to tailor the coefficient of thermal expansion (CTE) of composite to a specific positive, negative or even zero value. In this work, first‐principle calculations were performed to investigate the thermal expansion behavior in cordierite Mg₂Al₄Si₅O₁₈, which is a representative silicate widely used in the ceramic industry and of promising application due to its ultralow CTE and good thermal shock resistance. According to the quasi‐harmonic approximation and the Grüneisen theory, temperature dependences of linear CTEs along a, b, and c directions were predicted. The transverse acoustic modes and low‐energy optic modes are identified to take the most of the responsibility for the negative CTE, especially at low temperatures while the high‐energy optic modes contribute positively to the thermal expansion, leading to increasing CTE at higher temperatures. The ultralow linear CTEs result from the weighted average of all the modal contributions with negative or positive Grüneisen parameters. In addition, the anisotropy of thermal expansion originates from its layered crystal structure containing rigid tetrahedron rings in a‐b plane staking along c direction. This work provides an insight into the mechanism of ultralow and anisotropic thermal expansion in Mg₂Al₄Si₅O₁₈ and further enriches the scope of material design for use in applications needing to control thermal expansion.     

Preparation and properties of polyimide solvent‐resistant nanofiltration membrane obtained by a two‐step method

This study investigated the preparation of polyimide solvent‐resistant nanofiltration membranes by a two‐step method (casting the membrane first and then crosslinking by the thermal imidization method). The influences of polymer concentration, thickness of membranes, temperature of the imidization, phase inversion time and thermal imidization procedure were studied. The membranes with the highest rejection rate of Fast Green FCF (molecular weight 808.86 g mol^?1) were prepared in the following conditions: polymer concentration 13 wt%, phase inversion time 1 h, membrane thickness 150 µm and thermal imidization procedure 200 °C for 2.5 h, 250 °C for 2 h and 300 °C for 2 h in a vacuum environment; the heating rate was 5 °C min^?1. The membrane was stable in most of the solvents tested and the fluxes of some common solvents were equal to or higher than a number of commercial solvent‐resistant nanofiltration membranes. A much higher rejection of dyes in water than in methanol was observed in the filtration experiments and a new way to explain it was developed. Copyright © 2011 Society of Chemical Industry     

Synthesis and properties of polyimide (containing naphthalene) nanocomposites with organo‐modified montmorillonites

2,7‐Bis(4‐aminophenoxy) naphthalene (BAPN), a naphthalene‐containing diamine, was synthesized and polymerized with a 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) to obtain a polyimide (PI) via thermal imidization. To enhance the thermal and mechanical properties of the polymer, PI–Montmorillonite (MMT) nanocomposites were prepared from a DMAc solution of poly(amic acid) and a DMAc dispersion of MMT, which were organo‐modified with various amounts of n‐dodecylamine (DOA) or cetylpyridium chloride (CPC). FTIR, XRD, and TEM (transmission electron microscopy) were used to verify the incorporation of the modifying agents into the clay structure and the intercalation of the organoclay into the PI matrix. Results demonstrated that the introduction of a small amount of MMT (up to 5%) led to the improvement in thermal stability and mechanical properties of PI. The decomposition temperature of 5% weight loss (T_d,5%) in N₂ was increased by 46 and 36°C in comparison with pristine PI for the organoclay content of 5% with DOA and CPC, respectively. The nanocomposites were simultaneously strengthened and toughened. The dielectric constant, CTE, and water absorption were decreased. However, at higher organoclay contents (5–10%), these properties were reduced because the organoclay was poorly dispersed and resulted in aggregate formation. The effects of different organo‐modifiers on the properties of PI–MMT nanocomposite were also studied; the results showed that DOA was comparable with CPC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

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 polymerization of anthracene‐based itaconimides

Two new anthracene‐based itaconimides, ie N‐(1‐ and 2‐anthryl) itaconimides, were synthesized by the reaction of aromatic amines with itaconic anhydride, followed by itaconamic acid imidization. The same reaction failed in the case of anthracene‐ring substitution at the position 9′. Radical and thermal polymerization of N‐(1‐ and 2‐anthryl) itaconimides led to polymers with anthracene pendant groups. No self‐polymerization by Diels–Alder cycloaddition of the itaconic function (dienophile) and anthracene nucleus (diene) was observed, as is the case for N‐(anthryl) maleimides and citraconimides. Copyright © 2004 Society of Chemical Industry     

Effects of meta and para diamines on the properties of polyetherimide nanocomposite films prepared by the sol‐gel process

The effects of chemical structure of diamines on the properties of polyetherimide (PEI) nanocomposite films prepared by the sol‐gel process were investigated. For meta diamine, nanocomposites with improved thermal, mechanical, and dielectric properties can be prepared by a sol‐gel process from soluble PEI via chemical imidization, with silica content up to 10%. However, for the PEI with pPDA as diamine and bisphenol A dianhydride, a two‐stage sol‐gel process via thermal imidization was necessary to prepare the nanocomposites. The thermal stability and mechanical properties were improved with the addition of up to 5 wt % of silica content. The variation could be attributed to the fact that differences in the compatibility between PEI and SiO₂ for two kinds of PEI with the different meta and para structure of the diamine monomer. The morphology of the fracture surfaces investigated by SEM showed a finely interconnected or cocontinuous phase for PEI nanocomposites with the silica content of up to 10% and 5 wt % for mPDA and pPDA as diamine, respectively. At higher silica contents, thermal and mechanical properties were reduced due to the aggregation of SiO₂. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of chemical structure and preparation process on the aggregation structure and properties of polyimide film

In this article, polyimide (PI) films were fabricated via the three‐step method including the reactions of condensation polymerization, chemical imidization, and thermal imidization. In comparison with the conventional two‐step method to produce PI films, there was an additional step in the present method, i.e., chemical imidization. The aim of chemical imidization was to get PI intermediates with different pre‐imidization degree (pre‐ID). And PI component in PI intermediates acted as in‐situ rigid‐rod segments and induced orientation in the films of PI intermediates. Then the orientations of molecular chains were preserved in the following thermal imidization, and caused the difference in aggregation structure and property of the final PI films. The test results indicated that the orderly degree of molecular chains and mechanical properties of PI films increased with pre‐ID increasing. Furthermore, this tendency was much more obvious for more rigid backbone structure. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

In situ polymerization of polyimide‐based nanocomposites via covalent incorporation of functionalized graphene nanosheets for enhancing mechanical,thermal, and electrical properties

In this study, we report an effective method to fabricate high‐performance polyimide (PI)‐based nanocomposites using 3‐aminopropyltriethoxysilane functionalized graphene oxide (APTSi‐GO) as the reinforcing filler. APTSi‐GO nanosheets exhibit good dispersibility and compatibility with the polymer matrix because of the strong interfacial covalent interactions. PI‐based nanocomposites with different loadings of functionalized graphene nanosheets (FGNS) were prepared by in situ polymerization and thermal imidization. The mechanical performance, thermal stability, and electrical conductivity of the FGNS/PI nanocomposites are significantly improved compared with those of pure PI by adding only a small amount of FGNS. For example, a 79% improvement in the tensile strength and a 132% increase in the tensile modulus are achieved by adding 1.5 wt % FGNS. The electrical and thermal conductivities of 1.5 wt % FGNS/PI are 2.6 × 10^?3 S/m and 0.321 W/m·K, respectively, which are ～10¹⁰ and two times higher than those of pure PI. Furthermore, the incorporation of graphene significantly improves the glass‐transition temperature and thermal stability. The success of this approach provides a good rationale for developing multifunctional and high‐performance PI‐based composite materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42724.     

Processable conductive blends of polyaniline/polyimide

By using camphorsulfonic acid (CSA) to protonate polyaniline (PANI), the counterion enabled the PANI–CSA complex processable as a solution phase. So camphorsulfonic acid (CSA)-doped polyaniline/polyimide (PANI/PI) blend films were prepared by the solvent casting method using N-methylpyrrolidinone (NMP) as a cosolvent followed by thermal imidization. The conductivity of the PANI–CSA/PAA (50 wt % PANI content) is greater than that of the pure PANI sample at room temperature. As the thermal imidization proceeded, molecular order of polymer chain structure was improved in the resulting PANI–CSA/PI film due to the annealing effect of PANI chain, and this PANI–CSA/PI film showed higher conductivity than PANI–CSA and PANI–CSA/PAA film. PANI–CSA/PI blend films had a good thermal stability of conductivity at high temperature. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1863–1870, 1998     

Synthesis and properties of poly(ester imide) copolymers from 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 2,2′-bis(trifluoromethyl)benzidine,and 4-aminophenyl-4′-aminobenzoate

A series of poly(ester imide) (PEsI) copolymers were synthesized using 3,3′,4,4′-biphenyltetracarboxylic dianhydride (4,4′-BPDA), 2,2′-bis(trifluoromethyl)benzidine (TFMB), and 4-aminophenyl-4′-aminobenzoate (APAB) as the monomers. Wide-angle x-ray diffraction results revealed that the average interchain distances of these polymers ranged from 4.6 to 5.7 Å, increasing with the increase of TFMB contents. PEsI-0.3 and PEsI-0.4 exhibited a glass transition temperature (T_g) of 445 and 455°C, respectively, while no distinctive T_g was observed for the PEsI copolymers when the APAB content was >50 mol%. The coefficients of thermal expansion (CTE) of these PEsI copolymers ranged from 3.8 to 24.2 ppm K⁻¹, increasing with the increase of TFMB contents. The PEsI copolymers exhibited a modulus of 5.7–7.8 GPa, a tensile strength of 282–332 MPa, and an elongation-at-break of 10.2%–23.3%. Furthermore, these copolymers exhibited a dielectric constant of 2.53–2.76, and a low dissipation factor (D_f) of 0.0026–0.0032 at 10 GHz in dry state. Because of their excellent combined properties, these PEsI copolymers are promising candidates as dielectric substrate materials for the applications in next generation flexible printed circuit boards operating at high frequencies.     

The retarding effects and structural evolution of a bio-based high-performance polyimide during thermal imidization

The thermal imidization evolution of a bio-based high-performance polyimide, namely adenine-containing polyimide (API), was investigated by thermogravimetric analysis (TGA), in situ Fourier transform infrared spectroscopy (in situ FTIR), and wide-angle X-ray diffraction (WAXD), in contrast to an adenine-free 4,4′-oxydiphthalic anhydride (ODPA)/4,4′-oxydianiline (ODA) PI. The influence derived from adenine was focused. At precursor stage of API (polyamic acid, PAA), the H-bonding interaction of PAA–PAA type as well as the especial interaction between the secondary amine of adenine and solvent (dimethylacetamide, DMAc) was discovered. Structural evolution of API was traced by in situ FTIR and multistage WAXD from PAA stage to PI stage. Compared with OPI, the retarding effects were found in the process of thermal imidization of API, partly due to the formation of H-bonding derived from the extra secondary amine of adenine moieties, which complicated the H-bonding form in API. Finally, a hypothesis of evolution of thermal imidization process about API molecule was proposed in contrast with adenine-free ODPA ODA PI. Compared with the consistency of both API and ODPA ODA PI in PAA stage, API possessed a more delicate thermal imidization process. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46953.     

Organosoluble and light‐colored fluorinated polyimides based on 1,1‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐1‐phenylethane and various aromatic dianhydrides

To investigate the CF₃ group affecting the coloration and solubility of polyimides (PI), a novel fluorinated diamine 1,1‐bis[4‐(4‐amino‐2‐ trifluoromethylphenoxy)phenyl]‐1‐phenylethane (2) was prepared from 1,1‐ bis(4‐hydrophenyl)‐1‐phenylethan and 2‐chloro‐5‐nitrobenzotrifluoride. A series of light‐colored and soluble PI 5 were synthesized from 2 and various aromatic dianhydrides 3a–f using a standard two‐stage process with thermal 5a– f(H) and chemical 5a–f(C) imidization of poly(amic acid). The 5 series had inherent viscosities ranging from 0.55 to 0.98 dL/g. Most of 5a–f(H) were soluble in amide‐type solvents, such as N‐methyl‐2‐pyrrolidone (NMP), N,N‐ dimethylacetamide (DMAc), and N,N‐dimethylformamide (DMF), and even soluble in less polar solvents, such as m‐Cresol, Py, Dioxane, THF, and CH₂Cl₂, and the 5(C) series was soluble in all solvents. The GPC data of the 5a–f(C) indicated that the Mn and Mw values were in the range of 5.5–8.7 × 10⁴ and 8.5–10.6 × 10⁴, respectively, and the polydispersity index (PDI) Mw /Mn values were 1.2–1.5. The PI 5 series had excellent mechanical properties. The glass transition temperatures of the 5 series were in the range of 232–276°C, and the 10% weight loss temperatures were at 505–548 °C in nitrogen and 508–532 °C in air, respectively. They left more than 56% char yield at 800°C in nitrogen. These films had cutoff wavelengths between 356.5–411.5 nm, the b* values ranged from 5.0–71.1, the dielectric constants, were 3.11–3.43 (1MHz) and the moisture absorptions were in the range of 011–0.40%. Comparing 5 containing the analogous PI 6 series based on 1,1‐bis[4‐(4‐aminophenoxy)phenyl]‐1‐ phenylethane (BAPPE), the 5 series with the CF₃ group showed lower color intensity, dielectric constants, and better solubility. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2399–2412, 2005     

Polyimide fibers prepared by a dry‐spinning process: Enhanced mechanical properties of fibers containing biphenyl units

Polyimide (PI) fibers with enhanced mechanical properties and high thermal and dimensional stability were prepared via a two‐step dry‐spinning process through the introduction of 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride (BPDA) containing biphenyl units into rigid homopolyimide of pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline. The attenuated total reflectance–Fourier transform infrared spectra results imply that the incorporated BPDA moieties accelerate the imidization process and increase the imidization degree (ID) of the precursor fibers; this was attributed to the increased molecular mobility of the polymer chains. Two‐dimensional wide‐angle X‐ray diffraction spectra indicated that the prepared PI fibers possessed a well‐defined crystal structure and polymer chains in the crystalline region were highly oriented along the fiber axis. The PI fiber, with the molar ratio of PMDA/BPDA being 7/3, showed optimum tensile strength and modulus values of 8.55 and 73.21 cN/dtex, respectively; these were attributed to the high IDs and molecular weights. Meanwhile, the PI fibers showed better dimensional stability than the commercial P84 fiber, and this is beneficial for its security applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43727.     

Synthesis and characterization of benzimidazole‐based low CTE block copolyimides

A series of block and random copolyimide films were synthesized from various molar ratios of two diamines, rigid 2‐(4‐aminophenyl)‐5‐aminobenzimidazole (APBI) and flexible 4,4′‐oxydianiline (ODA) by polycondensation with dianhydride 3,3′,4,4′‐biphenyltetracarboxylic dianhydride. The contents of APBI ranged from 10 to 60 mol % in copolyimides. The copolyimide films obtained by thermal imidization of poly(amic acid) solutions, were characterized by TMA, DMA, TGA, DSC, wide‐angle X‐ray diffraction, FTIR, tensile testing, water uptake (WU), and dielectric constant measurements. Rigid heterocyclic diamine APBI with interchain hydrogen bonding capability, led to low coefficient of thermal expansion (CTE), high T_g, high thermal stability and better mechanical properties. Increasing the APBI mol % caused a gradual decrease in the CTE and increase in T_g, thermal stability and tensile strength properties of the copolyimides films. Moreover, significantly enhanced thermal and mechanical properties of the block copolyimides were also found as compared to random copolyimides. The block copolyimide with APBI content of 60 mol %, achieved excellent properties, that is, a low CTE (4.7 ppm/K), a high T_g at 377°C, 5% weight loss at 562°C and a tensile strength at 198 MPa. This can be interpreted because of comparatively higher degree of molecular orientation in block copolyimides. These copolyimides also exhibited better dielectric constant and WU. This combination of properties makes them attractive candidates for base film materials in future microelectronics. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Influence of graphene oxide on thermal,electrical, and morphological properties of new achiral polyimide

In this study, a new diamine N‐[2‐(1H‐indol‐3‐yl)ethyl]‐3,5‐diaminobenzamide (IEDAB) was synthesized using tryptamine as starting material and characterized by FT‐IR, ¹H‐NMR, ¹³C‐NMR, and mass spectroscopy. Then, it was polymerized with 3,3',4,4'‐benzophenone tetracarboxylic dianhydride (BTDA) via thermal imidization to produce polyimide (PI). A series PI/GO nanocomposite films were prepared by incorporating different ratios (1, 3, and 5 wt%) of synthesized GO by solution casting method. The synthesized PI was confirmed by Ubbelohde viscometer and FT‐IR spectroscopy. SEM and Raman spectroscopy showed that GO was well dispersed in the PI matrix. XRD patterns indicated the PI and PI/GO nanocomposite films were highly amorphous in nature. The synthesized PI and their nanocomposites show high thermal stability as their T_10% weight loss are in the range of 498 to 563°C with 30.6 to 40% of char yield and the glass transition temperatures (T_g s) are in the range of 188 to 262°C. The limited oxygen index (LOI) values increased from 31.4% to 56.0% with increases of 5% GO content in the PI/GO nanocomposite. They have high dielectric constant in the range of 2.6 to 5.1 at 1 MHz and also good mechanical properties with tensile strength of 81 to 116 MPa, elongation at break 5 to 9%. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers