Resistive switching characteristics of polyimides derived from 2,2′‐aryl substituents tetracarboxylic dianhydrides

2,2′‐Position aryl‐substituted tetracarboxylic dianhydrides including 2,2′‐bis(biphenyl)‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride and 2,2′‐bis[4‐(naphthalen‐1‐yl)phenyl)]‐4,4′,5,5′‐biphenyl tetracarboxylic dianhydride were synthesized. A new series of aromatic polyimides (PIs) were synthesized via a two‐step procedure from 3,3′,4,4′‐biphenyl tetracarboxylic dianhydride and the newly synthesized tetracarboxylic dianhydrides monomers reacting with 2,2′‐bis[4′‐(3″,4″,5″‐trifluorophenyl)phenyl]‐4,4′‐biphenyl diamine. The resulting polymers exhibited excellent organosolubility and thermal properties associated with T_g at 264 °C and high initial thermal decomposition temperatures (T_5%) exceeding 500 °C in argon. Moreover, the fabricated sandwich structured memory devices of Al/PI‐a/ITO was determined to present a flash‐type memory behaviour, while Al/PI‐b/ITO and Al/PI‐c/ITO exhibited write‐once read‐many‐times memory capability with different threshold voltages. In addition, Al/polymer/ITO devices showed high stability under a constant stress or continuous read pulse voltage of ? 1.0 V. Copyright © 2011 Society of Chemical Industry     

Low‐loss passive polymer waveguides by using chlorofluorinated polyimides

Chlorofluorinated polyimides were prepared from 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride (6FDA), 2,2′‐bis(trifluoromethyl)‐4,4′‐diaminobiphenyl (PFMB), and 2,2′‐dichloro‐4,4′‐diaminobiphenyl (DCB) for optical waveguide applications. The resulting optical polymers exhibited good thermal stability, controllable refractive index, and low optical loss in the optical communication wavelengths of 1.3 and 1.55 µm. The control of refractive indices of the polymers was achieved by copolymerization of 6FDA/PFMB and 6FDA/DCB. As the amount of DCB was increased, the refractive indices of polymer were increased. The effect of addition of chlorine on optical properties of polymers such as absorption loss in the near‐IR region were also investigated. Rib‐type optical waveguides were fabricated using these chlorofluorinated polyimides. These waveguides exhibited low loss of less than 0.4 dB/cm for both TE and TM polarizations. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 107–112, 1999     

Structural effects of pendant groups on thermal and electrical properties of polyimides

Two series of aromatic polyimides containing various‐sized alkyl side groups were synthesized by thermal imidization of the poly(amic acid)s prepared from the polyaddition of benzophenonetetracarboxylic dianhydride and hexafluoro‐isopropylidene bis(phthalic anhydride) with 4,4′‐methylenedianiline, 4,4′‐methylene‐bis(2,6‐dimethylaniline), 4,4′‐methylene‐bis(2,6‐diethylaniline), and 4,4′‐methylene‐bis(2,6‐diisopropylaniline). The extent to which alkyl substitutes affect the thermal properties of polyimides was examined by differential scanning calorimetry, thermomechanical analyzer, and thermogravimetric analysis techniques. The analytical results demonstrated that the incorporation of alkyl moieties causes a moderate increase in the coefficient of thermal expansion and a slight decrease in thermal stability. Notably, all polymers had a decomposition temperature exceeding 500°C. The glass transition temperature increases markedly when hydrogen atoms at ortho positions on aniline rings are replaced with methyl groups, but decreases with growing alkyl side group size. The dielectric measurements show that the polymer possessing a large alkyl side group would have the lower dielectric value. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4672–4678, 2006     

Organosoluble and light‐colored fluorinated polyimides derived from 5,5′‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy) phenyl]‐4,7‐methanohexahydroindan

A novel bis(ether amine) monomer, 5,5′‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐4,7‐methanohexahydroindan ( 2 ), was synthesized through the nucleophilic aromatic substitution reaction of 5,5′‐bis‐(4‐hydroxyphenyl)‐4,7‐methanohexahydroindan with 2‐chloro‐5‐nitrobenzotrifluoride to yield the intermediate dinitro compound, followed by catalytic reduction with hydrazine and Pd/C. A series of polyimides were synthesized from 2 and various aromatic dianhydrides using a standard two‐stage process with chemical or thermal imidization of poly(amic acid). All of these polymer films were soluble in amide‐type solvents above 10% w/v, had tensile strengths of 97–117 MPa, and the 10% weight loss temperature was above 464 °C with their residues exceeding 46% at 800 °C in nitrogen. Compared with the non‐fluorinated polyimides, the fluorinated series were observed to have lower dielectric constants (2.92–3.28 at 1 MHz) and lower moisture absorptions (0.15–0.43 wt%) as well as lower color intensity and better solubility. Copyright © 2006 Society of Chemical Industry     

Synthesis of a new diamine and its effect on the residual stress of colorless polyimide

A new diamine was designed and synthesized to improve the flexibility of colorless polyimides by reducing residual stress. Four variations of colorless polyimides with the same dianhydride (4,4′-(hexafluoroisopropylidene)-diphthalic) and four different diamines (bis[4-(3-aminophenoxy)-phenyl] sulfone, bis(3-aminophenyl) sulfone, 2,2′-bis(trifluoromethyl)benzidine, and 2,2-bis(4-aminophenyl)-hexafluoropropane) were used. A series of colorless polyimides were prepared by adding the new diamine. The carbon and ether bonds between the benzene rings of the new diamine affected the flexibility and optical properties of colorless polyimide. The synthesis of the new diamine was confirmed by NMR measurements. Furthermore, the decrease in residual stress at room temperature and the glass transition temperature was confirmed. The effect of the new diamine was most evident for polyimide with a bulky and rigid structure. Though a slight yellow color appears because of the broken charge transfer complex balance, controlling the content of the new diamine will allow application of polyimides in flexible display.     

Synthesis and properties of organosoluble polyimides derived from 2,2′‐dibromo‐ and 2,2′,6,6′‐tetrabromo‐4,4′‐oxydianilines

Two new aromatic diamines, 2,2′‐dibromo‐4,4′‐oxydianiline (DB‐ODA 4 ) and 2,2′,6,6′‐tetrabromo‐4,4′‐oxydianiline (TB‐ODA 5 ), have been synthesized by oxidation, bromination, and reduction of 4,4′‐oxydianiline (4,4′‐ODA). Novel polyimides 6a–f and 7a–f were prepared by reacting DB‐ODA ( 4 ) and TB‐ODA ( 5 ) with several dianhydrides by one‐step method, respectively. The inherent viscosities of these polyimides ranged from 0.31 to 0.99 dL/g (0.5 g/dL, in NMP at 30°C). These polyimides showed enhanced solubilities compared to those derived from 4,4′‐oxydianiline and corresponding dianhydrides. Especially, polyimides 7a , derived from rigid PMDA and TB‐ODA ( 5 ) can also be soluble in THF, DMF, DMAc, DMSO, and NMP. These polyimides also exhibited good thermal stability. Their glass transition temperatures measured by thermal mechanical analysis (TMA) ranged from 251 to 328°C. When the same dianhydrides were used, polyimides 7 containing four bromide substituents had higher glass transition temperatures than polyimides 6 containing two bromide substituents. The effects of incorporating more polarizable bromides on the refractive indices of polyimides were also investigated. The average refractive indices (n_av) measured at 633 nm were from 1.6088 to 1.7072, and the in‐plane/out‐of‐plane birefringences (Δn) were from 0.0098 to 0.0445. It was found that the refractive indices are slightly higher when polyimides contain more bromides. However, this effect is not very obvious. It might be due to loose chain packing resulted from bromide substituents at the 2,2′ and 2,2′,6,6′ positions of the oxydiphenylene moieties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Organosoluble polyimides derived from asymmetric 2‐substituted‐and 2,2′,6‐trisubstituted‐4,4′‐oxydianilines

We report a new method for the preparation of asymmetric diamines using 4,4′‐oxydianiline (4,4′‐ODA) as the starting material. By controlling the equivalents of bromination agent, N‐bromosuccinimide, we were able to attach bromide and phenyl substituents at the 2‐ or 2,2′,6‐positions of 4,4′‐ODA. Thus, four new asymmetric aromatic diamines, 2‐bromo‐4,4′‐oxydianiline (6), 2,2′,6‐tribromo‐4,4′‐oxydianiline (7), 2‐phenyl‐4,4′‐oxydianiline (8) and 2,2′,6‐triphenyl‐4,4′‐oxydianiline (9), were synthesized by this method. Their structural asymmetry was confirmed using ¹H NMR spectroscopy. Asymmetric polyimides (PI10–PI13) were prepared from these diamines and three different dianhydrides (pyromellitic dianhydride (PMDA), 3,3′,4,4′‐biphenyltetracarboxylic dianhydride and 2,2‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride) in refluxing m‐cresol. The formed polyimides, except PI10a derived from 6 and PMDA, were all soluble in m‐cresol without premature precipitation during polymerization. These polyimides with inherent viscosity of 0.41–0.96 dL g^?1, measured at a concentration of 0.5 g dL^?1 in N‐methyl‐2‐pyrrolidone at 30 °C, can form tough and flexible films. Because of the structural asymmetry, they also exhibited enhanced solubility in organic solvents. Especially, polyimides PI11a and PI13a derived from 7 and 9 with rigid PMDA were soluble in various organic solvents at room temperature. The structural asymmetry of the prepared polyimides was also evidenced from ¹H NMR spectroscopy. In the ¹H NMR spectrum of PI11a, the protons of pyromellitic moiety appeared in an area ratio of 1:2:1 at three different chemical shifts, which were assigned to head‐to‐head, head‐to‐tail and tail‐to‐tail configurations, respectively. These polyimides also exhibited good thermal stability. Their glass transition temperatures ranged from 297 to 344 °C measured using thermal mechanical analysis. © 2013 Society of Chemical Industry     

Relationship between the gas transport properties and the refractive index in high‐free‐volume fluorine‐containing polyimide membranes

The refractive index and gas transport properties (i.e., permeability, diffusivity, and solubility) in the 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride (6FDA)‐based polyimides were systematically investigated in terms of their polymer fractional free volumes (FFVs). The permeability and diffusion coefficients of the 6FDA‐based polyimide membranes to hydrogen, oxygen, nitrogen, methane, and carbon dioxide were correlated with their FFVs, which were estimated with van Krevelen's group contribution method. Linear correlations were also observed between the gas transport properties and the refractive index of these polyimides. We described FFV as a function of the refractive index based on the Lorentz–Lorenz equation. Linear correlations were observed between their refractive‐index‐based FFVs and the gas permeability, diffusivity, and solubility coefficients of these 6FDA‐based polyimides membranes. However, the FFVs of the 6FDA‐based polyimides calculated from refractive index were 1.16–1.37 times larger than their FFV values. This FFV was dependent on the free‐volume space and optical factors, such as the refractive index and molar refraction, which affected the electronic structure and the interactions between the gas molecules and the polymer segments. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Highly refractive polyimides containing pyridine and sulfur units: synthesis and thermal,mechanical, solubility and optical properties

Two series of isomers containing pyridine and sulfur unit aromatic diamine monomers, 4,4′‐bis(5‐amino‐2‐pyridinylsulfanyl)diphenyl sulfide ( 2a ), 4,4′‐bis(6‐amino‐3‐pyridinylsulfanyl)diphenyl sulfide ( 2b ) and 4,4′‐bis(5‐amino‐6‐methyl‐2‐pyridinylsulfanyl)diphenyl sulfide ( 2c ), 4,4′‐bis(5‐amino‐4‐methyl‐2‐pyridinylsulfanyl)diphenyl sulfide ( 2d ), were designed and synthesized. Aimed at clarifying the structure–property relationships of pyridine‐ and sulfur‐containing high refractive polymers, 2a was polymerized with various dianhydrides to prepare polyimides PI ‐1?PI ‐7 and 2b , 2c , 2d were reacted with 4,4′‐[p ‐thiobis(phenylenesulfanyl)]diphthalic anhydride to prepare polyimides PI ‐8?PI ‐10. The polyimides showed excellent optical properties with average refractive indices ranging from 1.7006 to 1.7620 and birefringence as low as 0.0056. Meanwhile, comparative studies on their properties including solubility, thermal and mechanical, and optical transparency properties were performed. Some property differences of the isomers caused by the sequence changes were found. © 2017 Society of Chemical Industry     

Preparation and characterization of organosoluble polyimides based on 1,1-bis[4-(3,4-aminophenoxy)phenyl]cyclohexane and commercial aromatic dianhydrides

A bis(ether amine) III-A containing a cyclohexane cardo group, 1,1-bis[4-(4-aminophenoxy)phenyl]cyclohexane, was synthesized and used as a monomer to prepare polyimides VI-A with six commercial dianhydrides via three different procedures. The intermediate poly(amic acid)s had inherent viscosities of 0.83–1.69 dL g⁻¹ and were thermally or chemically converted into polyimides. Polyimides were also prepared by high-temperature direct polymerization in m-cresol and had inherent viscosities higher than the thermally or chemically cyclodehydrated ones. To improve the solubility of polyimides, six copolyimides were also synthesized from bis(ether amine) III-A with a pair of dianhydrides, which contained 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride or 4,4′-hexafluoroisopropylidenediphthalic anhydride. Series VI-A polyimides were characterized by the good physical properties of their film-forming ability, thermal stability, and tensile properties. A comparative study of the properties, with the corresponding polyimides derived from 2,2-bis[4-(4-aminophenoxy)phenyl]propane, is also presented. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2750–2759, 2001     

Synthesis and characterization of organosoluble and transparent polyimides derived from trans‐1,2‐bis(3,4‐dicarboxyphenoxy)cyclohexane dianhydride

A novel dianhydride, trans‐1,2‐bis(3,4‐dicarboxyphenoxy)cyclohexane dianhydride (1,2‐CHDPA), was prepared through aromatic nucleophilic substitution reaction of 4‐nitrophthalonitrile with trans‐cyclohexane‐1,2‐diol followed by hydrolysis and dehydration. A series of polyimides (PIs) were synthesized from one‐step polycondensation of 1,2‐CHDPA with several aromatic diamines, such as 2,2′‐bis(trifluoromethyl)biphenyl‐4,4′‐diamine (TFDB), bis(4‐amino‐2‐trifluoromethylphenyl)ether (TFODA), 4,4′‐diaminodiphenyl ether (ODA), 1,4‐bis(4‐aminophenoxy)benzene (TPEQ), 4,4′‐(1,3‐phenylenedioxy)dianiline (TPER), 2,2′‐bis[4‐(3‐aminodiphenoxy)phenyl]sulfone (m‐BAPS), and 2,2′‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]sulfone (6F‐BAPS). The glass transition temperatures (T_gs) of the polymers were higher than 198°C, and the 5% weight loss temperatures (T_d5%s) were in the range of 424–445°C in nitrogen and 415–430°C in air, respectively. All the PIs were endowed with high solubility in common organic solvents and could be cast into tough and flexible films, which exhibited good mechanical properties with tensile strengths of 76–105 MPa, elongations at break of 4.7–7.6%, and tensile moduli of 1.9–2.6 GPa. In particular, the PI films showed excellent optical transparency in the visible region with the cut‐off wavelengths of 369–375 nm owing to the introduction of trans‐1,2‐cyclohexane moiety into the main chain. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42317.     

Synthesis and characterization of new soluble and thermostable polyimides via novel diisocyanates

A facile synthesis of two novel diisocyanates containing methylene groups and preformed imide structure is described. Furthermore, six thermally stable and soluble polyimides were synthesized by polycondensation of these two diisocyanates with pyromellitic dianhydride (PMDA), 3, 3 ′,4, 4 ′‐benzophenonetetracarboxylic dianhydride (BTDA) and hexafluoroisopropylidene‐2,2‐bis‐(phthalic anhydride) (6FDA) in N,N ‐dimethyl acetamide. All monomers and polymers were characterized by conventional methods and their physical properties such as solution viscosity, solubility properties, thermal stability and thermal behaviour were studied. © 1999 Society of Chemical Industry     

Synthesis and characterization of novel aromatic poly(amide‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl or 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic diamines

New aromatic diimide‐dicarboxylic acids having kinked and cranked structures, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b), were synthesized by the reaction of trimellitic anhydride with 2,2′‐bis(4‐aminophenoxy)biphenyl (1a) and 2,2′‐bis(4‐aminophenoxy)‐1,1′‐binaphthyl (1b), respectively. Compounds 2a and 2b were characterized by FT‐IR and NMR spectroscopy and elemental analyses. Then, a series of novel aromatic poly(amide‐imide)s were prepared by the phosphorylation polycondensation of the synthesized monomers with various aromatic diamines. Owing to structural similarity, and a comparison of the characterization data, a model compound was synthesized by the reaction of 2b with aniline. The resulting polymers with inherent viscosities of 0.58–0.97 dl g^?1 were obtained in high yield. The polymers were fully characterized by FT‐IR and NMR spectroscopy. The ultraviolet λ_max values of the poly(amide‐imide)s were also determined. The polymers were readily soluble in polar aprotic solvents. They exhibited excellent thermal stabilities and had 10% weight loss at temperatures above 500 °C under a nitrogen atmosphere. Copyright © 2003 Society of Chemical Industry     

Synthesis and properties of fluoro‐polyetherimides

A series of amorphous fluoro‐polyetherimides based on 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluropropane dianhydride (6FDA) and di‐ether‐containing diamines 4,4′‐bis(3‐aminophenoxy)diphenyl sulfone (m‐SED), 4,4′‐bis(4‐aminophenoxy)diphenyl sulfone (p‐SED), 4,4′‐bis(4‐aminophenoxy)diphenyl propane (BPADE) were synthesized. These melt processable polyetherimide polymers from p‐SED and BPADE showed excellent electrical properties. The dielectric constants, 2.74 and 2.65 at 10 MHz respectively, are lower than commercially available polyetherimide ULTEM® 1000, and polyimide Kapton® H films. In addition, we found that trifluoromethyl groups‐containing polyimides not only show extraordinary electrical properties, but they also exhibit excellent long‐term thermo‐oxidative stability and reduced water absorption relative to non‐fluorinated polyimides. The weight retention of these fluoro‐polyetherimides at 315°C for 300 h in air varies from 93% to 98%. Whereas, their moisture absorption at 100 RH at 50°C was in the range of 0.3% to 1.05%, which is much lower than those of Ultem 1000 and Kapton H. In the case of fluoro‐polyetherimides from p‐SED and m‐SED (para and meta isomers) diamines with ‘ether’ and sulfonyl (‐SO₂‐) spacer groups, the d‐spacing and T_g values decreased from 4.72Å to 4.56Å and 293°C to 244°C respectively. Similarly, the transparency of these polymer films (in the range of 80% to 90%) at 500 nm solar wavelength was higher than Ultem 1000 and Kapton H.     

Synthesis and properties of new aromatic polyimides based on 2,2′‐dibromo‐4,4′,5,5′‐benzophenone tetracarboxylic dianhydride

New polyimides with enhanced thermal stability and high solubility were synthesized in common organic solvents from a new dianhydride, 2,2′‐dibromo‐4,4′,5,5′‐benzophenone tetracarboxylic dianhydride (DBBTDA). DBBTDA was used as monomer to synthesize polyimides by using various aromatic diamines. The polymers were characterized by IR and NMR spectroscopy and elemental analysis. These polyimides had good inherent viscosities in N‐methyl‐2‐pyrrolidinone (NMP) and also high solubility and excellent thermo‐oxidative stability, with 5 % weight loss in the range 433 to 597 °C. Copyright © 2004 Society of Chemical Industry     

Synthesis and thermal,mechanical and gas permeation properties of aromatic polyimides containing different linkage groups

Two series of aromatic polyimides containing various linkage groups based on 2,7‐bis(4‐aminophenoxy)naphthalene or 3,3′‐dimethyl‐4,4′‐diaminodiphenylmethane and different aromatic dianhydrides, namely 4,4′‐(4,4′‐isopropylidenediphenoxy)bis(phthalic anhydride), 4,4′‐(hexafluoroisopropylidene)bis(phthalic anhydride), 3,3′,4,4′ benzophenonetetracarboxylic dianhydride, 9,9‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]fluorene dianhydride and 4,4′‐(4,4′‐hexafluoroisopropylidenediphenoxy)bis(phthalic anhydride), were synthesized and compared with regard to their thermal, mechanical and gas permeation properties. All these polymers showed high thermal stability with initial decomposition temperature in the range 475–525 °C and glass transition temperature between 208 and 286 °C. Also, the polymer films presented good mechanical characteristics with tensile strength in the range 60–91 MPa and storage modulus in the range 1700–2375 MPa. The macromolecular chain packing induced by dianhydride and diamine segments was investigated by examining gas permeation through the polymer films. The relationships between chain mobility and interchain distance and the obtained values for gas permeability are discussed. © 2014 Society of Chemical Industry     

Synthesis and property measurements of polyimides with substituted pyromellitic dianhydride for flexible printed circuits applications

Pyromellitic dianhydride‐based dianhydrides with bulky substituents, such as 1‐phenyl pyromellitic dianhydride and 1‐(4′‐trifluoromethylphenyl)pyromellitic dianhydride, were combined with bis(3‐aminophenyl)phenylphosphine oxide and 4,4′‐phenylene diamine to prepare polyimides with low coefficient of thermal expansion (～ 17 ppm/°C) and good adhesion (>100 g/mm). The polyimides were synthesized via a conventional two‐step process: preparation of poly(amic‐acid) followed by solution imidization with o‐dichlorobenzene. The molecular weights of the polyimides were controlled to 25,000 g/mol via off‐stoichiometry and the synthesized polyimides were characterized by Fourier transform infrared, nuclear magnetic resonance, differential scanning calorimetry, and thermogravimetric analysis. Their intrinsic viscosity and solubility were also measured, while adhesive property was measured via T‐peel test samples of Cu/polyimide. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Relationship between gas transport properties and fractional free volume determined from dielectric constant in polyimide films containing the hexafluoroisopropylidene group

The dielectric constant and gas transport properties (i.e., permeability, diffusivity, and solubility) in 2,2′‐bis(3,4‐dicarboxyphenyl)hexafluoropropane dianhydride (6FDA)‐based polyimides were systematically investigated in terms of their polymer fractional free volumes (FFVs) at 30°C. The permeability and diffusion coefficients of the 6FDA‐based polyimide films to hydrogen, oxygen, nitrogen, methane, and carbon dioxide were correlated with their FFVs estimated using van Krevelen's group contribution method. There appeared, however, small linear correlation coefficients. Linear correlations were also observed between the gas transport properties and dielectric constant of these polyimides. This study described FFVas a function of the dielectric constant based on the Clausius‐Mossotti equation. It was found that the gas permeability and diffusion coefficients of these 6FDA‐based polyimide films increased as their dielectric constant‐based FFV increased. A better linear relationship was observed between the gas transport properties and the FFV determined from the polymer dielectric constant in comparison to that estimated using the group contribution method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Comparative study of silicon‐containing polyimides from different oxydianilines

Silicon‐containing polyimides were synthesized by solution polycondensation of bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride with 3,4‐oxydianiline and 4,4′‐oxydianiline, respectively. All the poly(amic acid) films could be obtained by solution‐casting from N,N‐dimethylacetamide solutions and thermally converted into transparent and tough polyimide films. The physical properties of thin films of those polyimides were compared by DSC, TGA, UV–visible spectroscopy, and dynamic mechanical analysis. The polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 3,4‐oxydianiline exhibited superior energy‐damping characteristic, mechanical properties, and optical transparency, whereas that from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 4,4′‐oxydianiline possessed higher glass‐transition temperature and thermal stability. Because of the unsymmetric structure of the polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 3,4‐oxydianiline, its increasing rate of linear coefficient of thermal expansion with temperature was quicker than that of the polyimide from bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride and 4,4′‐oxydianiline. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2363–2367, 2004     

Adhesion property of novel polyimides with 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride

Novel polyimides were synthesized from 1‐[3′,5′‐bis(trifluoromethyl)phenyl] pyromellitic dianhydride (6FPPMDA) by a conventional two‐step process: the preparation of poly(amic acid) followed by solution imidization via refluxing in p‐chlorophenol. The diamines used for polyimide synthesis included bis(3‐aminophenyl)‐3,5‐bis(trifluoromethyl)phenyl phosphine oxide, bis(3‐aminophenyl)‐4‐trifluoromethylphenyl phosphine oxide, and bis(3‐aminophenyl)phenyl phosphine oxide. The synthesized polyimides were designed to have a molecular weight of 20,000 g/mol by off‐stoichiometry and were characterized by Fourier transform infrared, NMR, differential scanning calorimetry, and thermogravimetric analysis. In addition, their intrinsic viscosity, solubility, water absorption, and coefficient of thermal expansion (CTE) were also measured. The adhesion properties of the polyimides were evaluated via a T‐peel test with bare and silane/Cr‐coated Cu foils, and the failure surfaces were investigated with scanning electron microscopy. The 6FPPMDA‐based polyimides exhibited high glass‐transition temperatures (280–299°C), good thermal stability (>530°C in air), low water absorption (1.46–2.16 wt %), and fairly low CTEs (32–40 ppm/°C), in addition to good adhesion properties (83–88 g/mm) with silane/Cr‐coated Cu foils. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1801–1809, 2005