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     

Synthesis of aliphatic–aromatic polyimides by two-step polymerization of aliphatic dianhydride and aromatic diamine

Aliphatic-aromatic polyimides were synthesized by polycondensation reaction in solvent. The effects of variables such as the kind of solvent, reaction time and temperature, and monomer concentration were investigated in detail on the reaction of 1,2,3,4-butanetetra-carboxylic dianhydride and 4,4′-diaminodiphenylmethane. The viscos-ities of polyimides were between 0.22 and 0.46 dL/g. The polyimides were soluble in some aprotic polar solvents, such as N,N′-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), dimethylsulfoxide (DMSO), and N,N′-dimethylformamide (DMF). They began to decompose at 380–410°C in air, and 10% weight loss temperatures were 430–450°C. © 1996 John Wiley & Sons, Inc.     

Polymaleamide–polymaleimide networks

Polymaleamide–polymaleimide networks were obtained as films by the thermal treatment of mixtures with different ratios of an aliphatic–aromatic polymaleamide (PMA) and 4,4′‐bis(maleimidodiphenylmethane) (BMI), in N‐methyl‐2‐pyrolidinone (NMP) as a solvent. The polymaleamides were synthesized by ring‐opening polyaddition of 1,6‐hexamethylene–bisisomaleimide with 4,4′‐diaminodiphenylmethane in NMP at room temperature. The networks are infusible and insoluble in organic solvents; therefore, they were studied by solid‐state techniques such as IR, DSC, thermooptical analysis (TOA), TG/DTG analysis, and TEM. Thermal treatment of pure PMA and BMI occurs with the formation of crosslinked structures as proved by IR spectra. DSC and TOA curves show the appearance of chemical interactions between PMA and BMI in cured films and the formation of ordered morphologies, especially when BMI is the major component. TG/DTG and TEM results supported these observations. The PMA–polymaleimide network films present electrical insulator properties superior to individual polyamides or polyimides. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 779–788, 2004     

Preparation of organo‐soluble co‐polyimides using N‐methyl‐2‐pyrrolidone as the solvent via one‐pot high‐temperature polymerization

A series of organo‐soluble co‐polyimides (co‐PIs) were successfully synthesized from 3,3′,4,4′‐benzophenonetetracarboxylic‐dianhydride (BTDA), 1,4‐bis‐(4‐amino‐2‐trifluoromethyl‐phemoxy)‐benzene (p‐6FAPB) and 2‐(4‐aminophenyl)‐5‐aminobenzimidazole (BIA) via the one‐pot high‐temperature polymerization using N‐methyl‐2‐pyrrolidone (NMP) as the solvent. The imidization reaction of poly(amic acid)s in solution state was discussed in detail by attenuated total reflectance‐Fourier transform infrared spectra (ATR‐FTIR), and the results illustrate that the introduced benzimidazole moiety has a catalytic activity on the imidization process. The number‐average molecular weights and polydispersity index of these PIs measured by gel permeation chromatography range from 1.11 × 10⁵ to 2.20 × 10⁵ and 1.82 to 3.84, respectively. The prepared co‐PIs exhibit sufficient solubility in some polar solvents and high optical transparency. Meanwhile, these co‐PI films show good mechanical performances, and the strength and modulus of the sample with the molar ratio of p‐6FAPB/BIA = 5/5 reach 183 MPa and 4.71 GPa, respectively. Moreover, the obtained co‐PIs possess high glass transition temperatures (T_g) (above 260 °C) and good thermal stability with 5% weight loss temperature in the range of 502–531 °C in the nitrogen atmosphere. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45497.     

Preparation of Transparent Polyimides Derived from cis‐ and trans‐Dicyclohexyl‐3,3′,4,4′‐tetracarboxylic Dianhydrides

Two series of alicyclic polyimides composed of cis‐ and trans‐dicyclohexyl‐3,3′,4,4′‐tetracarboxylic dianhydrides (DCDAs) and aromatic diamines were prepared. All cis‐polymers could be readily prepared both in a one‐step method and a two‐step method. However, a two‐step method is preferably applied in the preparation of trans‐polymers, because in a one‐step method the trans‐configuration is partially lost at higher temperatures. These polyimide solutions could be cast into tough and flexible films, which were characterized by inherent viscosity, GPC, DSC, TGA measurements, and UV‐vis spectroscopy. The glass transition temperatures (T_g's) of the polymers were in the range of 210–270°C and the 5% weight loss temperatures were around 480°C for all PIs prepared. The optical transmittances of these films were more than 80% at 350 nm for ca. 15 μm thickness.     

Synthesis of soluble and thermally stable polyimides from 3,5‐diamino‐N‐(4‐(8‐quinolinoxy) phenyl) aniline and various dianhydrides

Three novel polyimides (PIs) having pendent 4‐(quinolin‐8‐yloxy) aniline group were prepared by polycondensation of a new diamine with commercially available tetracarboxylic dianhydrides, such as pyromellitic dianhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and bicyclo[2.2.2]‐oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride. These PIs were characterized by FTIR, ¹H NMR, and elemental analysis; they had high yields with inherent viscosities in the range of 0.4–0.5 dl g⁻¹, and exhibited excellent solubility in many organic solvents such as N,N‐dimethyl acetamide, N,N′‐dimethyl formamide, N‐methyl pyrrolidone (NMP), dimethyl sulfoxide, and pyridine. These PIs exhibited glass transition temperatures (T_g) between 250 and 325° C. Their initial decomposition temperatures (T_i) ranged between 270 and 450°C, and 10% weight loss temperature (T₁₀) up to 500°C with 68% char yield at 600°C under nitrogen atmosphere. Transparent and hard polymer films were obtained via casting from their NMP solutions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

一类含甲基结构高透明聚酰亚胺的合成与性能研究

以2,6-二氨基甲苯、3,3'',4,4''-联苯四甲酸二酐、3,3'',4,4''-二苯醚四甲酸二酐为原料，间甲酚作为溶剂，经一步法高温共缩聚，制备一系列可溶性共聚型聚酰亚胺(MPI)。利用红外光谱（FTIR）、核磁共振波谱（1H NMR）、差式扫描量热仪（DSC）、热重分析仪（TGA）和紫外-可见光分度计（UV）等测试仪器对MPI进行结构与性能表征。结果表明：红外与核磁的数据说明成功合成了含甲基结构的聚酰亚胺；该系列的含甲基聚酰亚胺在室温下可溶于N-甲基吡咯烷酮（NMP）、N,N-二甲基乙酰胺（DMAc）、二氯甲烷（CH2Cl2）三氯甲烷（CHCl3）、二甲基亚砜（DMSO）等有机溶剂，具有良好的溶解性和成膜性，并随着联苯酐的含量增加溶解性降低；同时该系列MPI制得的薄膜具有良好的光学透过性能，在紫外光波长450 nm时的透过率均在74%以上，截止波长在350 nm左右；该系列MPI的起始分解温度均大于457 ℃，800 ℃氮气氛围中的焦炭产率均大于63%，玻璃化转变温度在260 ℃~285 ℃之间，表现出优异的热学性能。此外，MPI-1~MPI-4薄膜还具有良好的机械性能，其弹性模量在1.7~2.1 GPa，拉伸强度在89.7~120.6 MPa，断裂伸长率在19.7%~28.4%。     

Synthesis,characterization, thermal and optical properties of soluble polyimides derived from an unsymmetrical diamine

A new unsymmetrical diamine monomer, 2,4‐diaminophenyl [4′‐(2′′,6′′‐diphenyl‐4′′‐pyridyl)phenyl]ether, was successfully synthesized by nucleophilic substitution of 1‐chloro‐2,4‐dinitrobenzene with 4‐(2′,6′‐diphenyl‐4′‐pyridyl) phenol. The diamine monomer was characterized by FTIR, ¹H and ¹³C NMR, and elemental analysis techniques and used for the preparation of novel polyimides (PIs) by reaction with commercially available tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride, and bicyclo[2.2.2]‐oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride. These PIs with inherent viscosities ranged from 0.43 to 0.48 dL/g were readily soluble in many organic solvents and afforded tough and flexible films by solution casting. These polymers exhibited T_gs between 237 and 294°C, and 10% weight loss temperatures in excess of 500°C with up to 56% char yield at 600°C in air. Their maximum fluorescence emission in dilute (0.2 g/dL) NMP solution appeared at 450 nm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Preparation and Properties of Cyano-Containing Polyimide Films Based on 2,6-Bis(4-aminophenoxy)- benzonitrile

Summary A series of cyano-containing polyimides were synthesized from 2,6-bis(4-amino- phenoxy)benzonitrile and some aromatic dianhydride monomers by solution polycondensation. The poly(amic acid) films could be obtained by solution-cast from N-methyl-2-pyrrolidinone solutions and thermally converted into tough polyimide films. Structure and physical properties of thin films of those polyimides were measured by FTIR, TGA, dynamic mechanical analysis and LCR hitester et al. Results showed that the polyimides prepared from 2,6-bis(4-aminophenoxy)- benzonitrile and 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride or 4,4’-(hexafluoropropylidene)diphthalic anhydride exhibited more excellent energy-damping characteristic and excellent solubility in NMP, DMF, DMAc, DMSO, THF and CHCl₃, whereas the polyimides from 2,6-bis(4-aminophenoxy)benzonitrile and 3,3’,4,4’-biphenyltetracarboxylic dianhydride or Pyromellitic dianhydride were insoluble in polar and nonpolar organic solvents. All polyimides indicated higher glass transition temperatures, excellent thermal stability and tensile properties. Incorporating a nitrile group into the polyimide backbone would enhance the dielectric constant of the polyimide films.     

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 characterization of fluorine and nitrile containing polyimides

A series of polyimides were synthesized from new diamine, Bis [4,4′‐amino‐5,5′ trifluoromethyl phenoxy‐(hexafluoro isopropylidine) phenoxy phenyl] benzonitrile [BATFB] and various aromatic tetracarboxylic anhydrides by thermal and chemical imidization routes. The BATFB was synthesized in two steps by nucleophilic displacement reaction of 2,6‐dichloro benzonitrile, 4,4′‐(hexafluoro isopropylidine) diphenol and 2‐amino‐5‐fluoro benzotrifluoride in the presence of anhydrous potassium carbonate in N,N′‐dimethyl acetamide (DMAc) and the structure was confirmed by FTIR spectroscopy and CHNSO analyzer. The polymers were characterized by FTIR spectroscopy and thermal analysis were performed by differential scanning calorimetry and thermogravimetric analysis methods. The prepared polyimides had glass transition temperatures between 230 and 290°C and their 10% weight loss were recorded in the range 550–590°C in N₂ atmosphere. Majority of polymers are found to be soluble in most of the organic solvents such as DMSO, DMF, DMAc, m‐cresol, and THF even at room temperature and few becomes soluble on heating. The prepared polyimides showed water uptake values 0.34–0.54 wt % at room temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3455–3461, 2006     

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 polyimide/hexagonal boron nitride composite

Polyimide (PI)/hexagonal boron nitride (h‐BN) composites were produced via the thermal imidization procedure from solution mixtures of a polyamicacid, which is prepared from 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride and 3,3′‐diaminodiphenyl sulfone (DADPS) in N‐methyl‐2‐pyrrolidone (NMP), and alkoxysilane functionalized h‐BN. The structure, thermostability, thermal behavior, and surface properties of the resulting materials were characterized by means of Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscopy (SEM). The thermal characteristics of PI/h‐BN films were better than the pure PIs. The physical and mechanical properties of the films were evaluated by various techniques such as contact angle, chemical resistance, and tensile tests. The flame retardancy of the composite materials was also examined by the limiting oxygen index (LOI). The experiments showed that the LOI values of PIs increased from 32 to 43 for the materials containing hexagonal boron nitride. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Correlation of pretilt angles and surface chemical structures of polyimide alignment films after direct fluorination

A series of polyimides (PIs) with side chains were fabricated from 6‐(4‐phenylphenoxy)hexyl‐3,5‐diaminobenzoate of various ratios with 4,4′‐oxydianiline and 4,4′‐oxydiphthalic anhydride. After PI alignment, films were directly fluorinated using a 10 vol% fluorine/nitrogen mix. The pretilt angle of liquid crystals on the PI films is much improved to more than 20°, and can be continuously controlled by changing the side‐chain content of the PI films from 20 to 100%. The change of the pretilt angles is ascribed to the fluorinated microstructure of molecules at the surface rather than to the surface energy or surface morphology. Moreover, the improvement of rigidity and the steric repulsion of the fluorinated side chains result in an upright conformation of the side chains that leads to the high pretilt angle. Copyright © 2010 Society of Chemical Industry     

A study of the stabilization of vertical alignment for liquid crystals by increasing the side‐chain rigidity of polyimides

A series of polyimides (PIs) with various side‐chain structures were prepared via copolymerization of pyromellitic dianhydride, 3,3′‐dimethyl‐4,4′‐methylenediamine and three functional diamines: 4‐(4‐octyloxybenzoyloxy)biphenyl‐3′,5′‐diaminobenzoate (C8‐BPDA), 4‐octyloxybiphenyl‐3′,5′‐diaminobenzoate (C8‐PDA) and 4‐(4‐butoxybenzoyloxy)biphenyl‐3′,5′‐diaminobenzoate (C4‐BPDA). PIs derived from C8‐BPDA and C4‐BPDA exhibited excellent rubbing resistance in comparison with PI from C8‐PDA and the pretilt angle could be controlled over 89° after rubbing. Thermogravimetric analysis showed that the thermal degradation of PIs under nitrogen atmosphere occurred above 320 °C, and PI derived from C8‐BPDA showed the best thermal stability. Wide‐angle X‐ray diffraction patterns indicated an amorphous morphology of the PIs, and the PIs also had outstanding solubility in polar aprotic solvents. The resultant PI films were light colored and maintained high transparency in the visible light region. By increasing the rigidity of side‐chains, the rubbing resistance and the thermal stability of PIs could be promoted at the same time. © 2012 Society of Chemical Industry     

Sulfonated polyimide copolymers based on 4,4′-diaminostilbene-2,2′-disulfonic acid and 3,5,3′,5′-tetramethylbenzidine with enhanced solubility

A new series of six-membered ring sulfonated polyimides with different combinations of two comonomers in the nonsulfonated diamine was prepared by one-step high-temperature polycondensation in m-cresol to improve the solubility of the resulting sulfonated polyimides. They are based on 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4′-diaminostilbene-2,2-disulfonic acid sulfonated diamine, and equimolar mixture of 3,5,3′,5′-tetramethylbenzidine (TMB) and 4,4′-oxydianiline, bis(4-aminophenyl)methane, or bis(4-(aminophenoxy)-4-phenyl)isopropylidene nonsulfonated diamines. The introduction of TMB comonomer in the nonsulfonated diamine resulted in a remarkable improvement in the solubility of the resulting polyimides in comparison with the corresponding single-monomer nonsulfonated diamine polyimides. Flexible, transparent, and tough membranes were prepared by solution casting method from the different polyimides. The membranes were characterized with FTIR and ¹H-NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, water uptake, and ion-exchange capacity measurements. They exhibit high thermal stability and good correlation between the ion-exchange capacity and water uptake values.     

Synthesis of a new siloxane‐containing alicyclic dianhydride and the derived polyimides with improved solubility and hydrophobicity

The structural transformation strategy of cis‐5‐norbornene‐endo‐2,3‐dicarboxylic anhydride (NA) was performed by esterification. The double bond on the diester of NA showed adequate hydrosilylation reactivity with Si? H bonds of phenyl‐containing disiloxane. Thereby, a new siloxane‐containing alicyclic dianhydride, 5,5′‐exo‐(1,3‐dimethyl‐1,3‐diphenyl‐disiloxane‐1,5‐diyl)bisbicyclo[2,2,1]heptane‐2,3‐endo‐dicarboxylic anhydride 6 was successfully synthesized starting from NA, 1,3‐dimethyl‐1,3‐diphenyldisiloxane and platinum complex catalyst. The whole synthetic route of dianhydride 6 consisted of esterification, hydrosilylation, saponification, acidification, and dehydration. A series of polyimides (PIs) were prepared from dianhydride comonomers of 6 and 4,4′‐biphenyltetracarboxylic dianhydride (BPDA) in different molar ratio together with the diamine 4,4′‐oxydianiline (ODA). The thermal and mechanical properties of PIs showed somewhat decrease with increasing content of dianhydride 6. The solubility of PIs increased with the increasing content of dianhydride 6, and further calculation from Bragg's equation indicated that average interchain distance (d‐spacing value) increased with increasing content of siloxane and alicyclic segments in the backbone of PIs. It was revealed that the hydrophobicity of PIs increased with the increasing content of dianhydride 6 . Polyimide 7g , which was prepared from 100% 6 and ODA, showed water adsorption of less than 0.7% and contact angle against water of 101.1°. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci., 2013     

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