Overview of emerging nonvolatile memory technologies

Nonvolatile memory technologies in Si-based electronics date back to the 1990s. Ferroelectric field-effect transistor (FeFET) was one of the most promising devices replacing the conventional Flash memory facing physical scaling limitations at those times. A variant of charge storage memory referred to as Flash memory is widely used in consumer electronic products such as cell phones and music players while NAND Flash-based solid-state disks (SSDs) are increasingly displacing hard disk drives as the primary storage device in laptops, desktops, and even data centers. The integration limit of Flash memories is approaching, and many new types of memory to replace conventional Flash memories have been proposed. Emerging memory technologies promise new memories to store more data at less cost than the expensive-to-build silicon chips used by popular consumer gadgets including digital cameras, cell phones and portable music players. They are being investigated and lead to the future as potential alternatives to existing memories in future computing systems. Emerging nonvolatile memory technologies such as magnetic random-access memory (MRAM), spin-transfer torque random-access memory (STT-RAM), ferroelectric random-access memory (FeRAM), phase-change memory (PCM), and resistive random-access memory (RRAM) combine the speed of static random-access memory (SRAM), the density of dynamic random-access memory (DRAM), and the nonvolatility of Flash memory and so become very attractive as another possibility for future memory hierarchies. Many other new classes of emerging memory technologies such as transparent and plastic, three-dimensional (3-D), and quantum dot memory technologies have also gained tremendous popularity in recent years. Subsequently, not an exaggeration to say that computer memory could soon earn the ultimate commercial validation for commercial scale-up and production the cheap plastic knockoff. Therefore, this review is devoted to the rapidly developing new class of memory technologies and scaling of scientific procedures based on an investigation of recent progress in advanced Flash memory devices.     

New fluorene‐based thermally stable five‐ and six‐membered rings polyimides with enhanced solubility

A novel ester diamine, 9‐(3,5‐diaminobenzoyloxy) fluorene, as a new monomer for preparation of polyimides was synthesized via two successive reactions. In the first step, reaction of 3,5‐dinitrobenzoylchloride with 9‐hydroxy fluorene in the presence of sodium hydroxide led to preparation of 9‐(3,5‐dinitrobenzoyloxy) fluorene. Second reaction was reduction of the nitro groups by tin (II) chloride and fuming hydrochloric acid to produce 9‐(3,5‐diaminobenzoyloxy) fluorene. The new diamine containing bulky fluorene group was characterized and polycondensed with different dianhydrides via two methods to produce polyimides. The new five‐membered and six‐membered ring polyimides were characterized and their properties including solubility behavior, inherent viscosity, thermal behavior and stability, and crystallinity were studied. They exhibited favorable balance of physical and thermal properties and their solubility were improved without sacrificing their thermal stability. Six‐membered rings polyimides showed higher thermal stability and lower solubility in comparison to related five‐membered ring polyimides. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on high performance nonvolatile polyimides coating: Gamma ray initiated bulk copolymerization of vinyl polar monomer and maleimide-terminated polyimides with flexible backbone and the modifications

The objective of the present work was to develop a nonvolatile coating involving vinyl polar monomer and high performance maleimide-terminated polyimides (MTPs) with flexible backbone. The synthesized MTPs with different molecular weight (Mw) showed good solubility in N-vinylpyrrolidone (NVP), and the homogeneous binary systems were obtained even when the content of MTPs reached 50 wt%. NVP-MTPs copolymer resin were prepared by gamma ray initiated bulk copolymerization, followed by thermal postcuring to improve the properties. NVP-MTPs copolymer resins exhibited flexural strength higher than 76 MPa, glass transition (T_g) higher than 142 °C, thermal stability (T_5%) no less than 214 °C, but relatively poor impact strength and water resistance property. It was revealed that increasing Mw of MTPs would result in the increase of impact strength and a decrease of thermal and flexural properties of copolymer resin, accompanied with the gradual decrease of gel percentage of copolymer resin. Amino-terminated linear polyimide (ATLP) was introduced to modify NVP-MTPs copolymer resin and the C-N linkage was formed from terminal NH₂ to electron deficient double bone on maleimide ring of MTPs via Michael nucleophilic addition. Polyvinylsiloxane (PVS) were introduced to modify NVP-MTPs copolymer resin by in situ ring opening polymerization followed with copolymerization under gamma ray initiation. The introduction of both modifiers led to an appreciable increase of impact strength and a remarkable water uptake decrease, meanwhile, other properties including thermal and flexural properties of modified copolymer resins maintained and even exhibited a slight increase. Fracture surface morphology by scanning electron microscopy (SEM) technique showed that introduction of both modifiers maintained good homogeneity of copolymer resin, and led to a gradual transition from rigid deformation to plastic deformation.     

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     

Synthesis and characterization of new alkali-soluble polyimides and preparation of alternating multilayer nano-films therefrom

New alkali-soluble aromatic polyimides were prepared by a direct one-step polycondensation of 3,6-di(4-carboxyphenyl)pyromellitic dianhydride with common aromatic diamines in the presence of isoquinoline at 170 °C. The obtained polymers with inherent viscosities of the 0.62-1.01 g/dl range were all amorphous and highly soluble in dilute aqueous NaOH and tetramethylammonium hydroxide. Upon heating in TGA, the carboxylic acid groups degraded away at lower temperatures and the chain backbone did at higher temperatures. In DSC, no glass transition could be detected before decomposition. The alternating multilayer nano-films from the polyimides and poly(ethyleneimine) were prepared by the molecular self-assembly method and characterized by ellipsometry and X-ray reflectivity.     

Synthesis and photoconductive characteristics of biphenylporphyrin‐containing poly(amic acid)s and polyimides

Three series of biphenylporphyrin (BPP)‐containing poly(amic acid)s (PAAs) were synthesized and converted into heat‐treated polyimides (HPIs) and chemically treated polyimides (CPIs). Viscosity measurements, UV–vis and IR spectroscopies, as well as thermogravimetric analysis (TGA), were used to characterize the structures of the polymers. UV–vis spectra revealed that the BPP units formed aggregates in PAA and CPI films, rather than in HPI films. Photoinduced discharge was used to characterize the photoconductive properties of these polymer films. It was found that the photosensitivity was greatly enhanced by introducing BPP units into the polymer chains. For these three series of polymers, the photosensitivity increased in the order PAA < HPI < CPI according to the content of BPP in the polymers. The photoconductive characteristics were interpreted by the intrinsic π—π* process of BPP aggregation and the extrinsic process of charge‐transfer complex formation. The best photoconductive performances of the CPIs were attributed to the existence of two charge‐carrier‐generation processes. Copyright © 2004 Society of Chemical Industry     

Synthesis of highly transparent and thermally stable copolyimide with fluorine-containing dianhydride and alicyclic dianhydride

The development of optical films is highly desirable for applications in flexible displayers. In this work, a copolyimide (co-PI) film with high thermal stability and high transparency was prepared by the copolymerization of 2,2′-bis(trifluoromethyl)-4,4′-diaminodiphenyl ether, cyclobutanetetracarboxylic dianhydride, and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). The effects of aliphatic dianhydride and fluorine dianhydride monomers on the optical, thermal, and mechanical properties of the co-PIs were discussed in detail based on the experimental results and theoretical simulations. We found that the preparation of polyimide (PI) based on the combination of two dianhydrides could obtain the PI film with excellent comprehensive performance due to nonconjugated structure and strong electron-withdrawing effect. Through the structure and composition optimization, a PI film of PI-6FDA-70 with T_g of 300 °C, T_d10% more than 500 °C, the average transparency of 90% and the elongation at the breakage more than 8% was prepared. Such molecular design provides a practical approach to develop high-performance colorless PI films. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48603.     

Synthesis and characterization of some new thermally stable polyimides and copolyimides bearing bipyridine side-chain groups

A new series of polyimides and copolyimides were synthesized via reaction of new bipyridine containing diamine, 4, 6-bis(4-aminophenyl)-2, 2′-bipyridine, with commercial dianhydrides. 4, 6-bis(4-aminophenyl)-2, 2′-bipyridine was synthesized starting from condensation reactions of 4-nitro acetophenone, 4-nitrobenzadehyde and pyridacyl pyridinium iodide (Krönke salt) and reduction of the desired dinitro compound. The synthesized monomer and polymers were characterized by FT-IR, NMR and CHN elemental analysis. The physical properties of the polymers, including solubility and viscosity were studied, and the results showed acceptable solubility and good chain growth for polymers. Thermal stability of these polymers was also studied by Thermo Gravimetric Analysis (TGA). The polymers start to lose weight because of thermal degradation at about 300 °C. From Differential Scanning Calorimetry (DSC), the polymers were showed T_g between 190 and 230 °C. The morphology of these polymers was also investigated by X-ray Diffraction (XRD), and the results showed only broad reflections originated from their low crystallinities.     

Synthesis,thermal properties,and flame retardancy of phosphorus containing polyimides

Phosphorus containing polyimides were prepared via phosphorylation of organosoluble polyimides. This was achieved by phenoxaphosphine oxide ring formation reaction or esterification with diethylchlorophosphate. The phosphorylation was confirmed by infrared, ³¹P nuclear magnetic resonance, and elemental analysis for phosphorus. Polyimides containing phosphorus of 8.3 and 5.4% by weight were found. Thermal characteristics and decomposition behavior of the resulting polyimides were investigated by differential scanning calorimetry and thermogravimetric analysis. Introduction of phosphorus into polyimides slightly reduced their initial weight loss temperatures and led to high char yields at temperatures higher than 800°C. Limiting oxygen index values higher than 48 were found for the phosphorylated polyimides. Such properties make these polymers useful in flame retardant applications. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 875–882, 1997     

Fluorescent,electroactive, thermally stable triphenylamine‐ and naphthalene‐based polyimides for optoelectronic applications

To tune the photophysical properties of polyimides (PIs), a diamine containing naphthalene and triphenylamine units, N¹‐(4‐aminophenyl)‐N¹‐[(4‐naphthalene‐2‐yloxy)phenyl]benzene‐1,4‐diamine (DA), was synthesized. A series of fluorescent electroactive new PIs from synthesized DA were prepared with conventional thermal imidization with dianhydride. The selected dianhydride were used to study and compare the effects of rigid planar phenyl, flexible phenoxy, and nonplanar flexible hexafluoroisopropyidene and carbonyl groups in the main polymer backbone on the optoelectronic properties and processability of materials. The structures of the synthesized diamine and its PIs were evaluated by spectral and CHNS elemental analysis. The optoelectronic and thermal properties of PIs revealed intense blue‐light emission (428–477 nm), a low oxidation potential (0.3–1.3 V), and a lower highest occupied molecular orbital–lowest unoccupied molecular orbital gap (2.92–3.21 eV). The observed behavior and properties of our synthesized PIs suggest their potential as future hole‐transport materials in optoelectronic applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44526.     

Synthesis and memory characteristics of polyimides containing noncoplanar aryl pendant groups

A series of soluble aromatic polyimides were prepared from 2,2′-diphenyl-4,4′-biphenyl diamine (DPBD), 2,2′-bis(biphenyl)-4,4′-biphenyl diamine (BBPBD), 2,2′-bis[4-(naphthalen-1-yl)phenyl]-4,4′-biphenyl diamine (BNPBD) and 2,2′-bis(3,5-dimethoxyphenyl)-4,4′-biphenyl diamine (BMPBD) by polycondensation with 2,2′-bis[4′-(3′′,4′′,5′′-trifluorophenyl)phenyl]-4,4′,5,5′-biphenyl tetracarboxylic dianhydride via a two-step procedure. The resulting polymers were fully characterized and they exhibited excellent organosolubility, high thermal and dimensional stability. Resistive switching devices with the configuration of Al/polymer/ITO were constructed from these polyimides by using conventional solution coating process. Devices with the active layer based on DPBD, BBPBD and BNPBD exhibited nonvolatile and rewritable flash type memory characteristics with the turn-on voltage at ?2.0 to ?3.0 V and the turn-off voltage at 2.0–3.0 V. Whereas, device based on BMPBD demonstrated a bipolar write-once read-many times (WORM) memory capability with the writing voltage around ±3.0 V. The ON/OFF current ratio of these devices was of about 10⁶ and the retention times can be as long as 10⁴ s.     

Synthesis of highly soluble and transparent polyimides

A novel aromatic diamine, 3,3′‐diisopropyl‐4,4′‐diaminophenyl‐4″‐methyltoluene with a 4‐methylphenyl pendant group and isopropyl side groups, was designed and synthesized in this study. Then it was polymerized with various aromatic dianhydrides including pyromellitic dianhydride, 3,3′,4,4′‐biphenyltetracarboxylic dianhydride, 4,4′‐oxydiphthalic anhydride, 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride and 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride via a one‐pot high temperature polycondensation procedure to produce a series of aromatic polyimides. These polyimides exhibited excellent solubility even in common organic solvents, such as chloroform and tetrahydrofuran. The flexible and tough films can be conveniently obtained by solution casting. The films were nearly colorless and exhibited high optical transparency, with the UV cutoff wavelength in the range 302–365 nm and the wavelength of 80% transparency in the range 385–461 nm. Moreover, they showed low dielectric constants (2.73–3.23 at 1 MHz) and low moisture absorption (0.13%–0.46%). Furthermore, they also possessed good thermal and thermo‐oxidative stability with 10% weight loss temperatures (T_10%) in the range 489–507 °C in a nitrogen atmosphere. The glass transition temperatures of all polyimides are in the range 262–308 °C. Copyright © 2012 Society of Chemical Industry     

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 organosoluble polyimides based on novel flourene‐ring containing diacetamido‐diamine

A new diacetamido‐diamine monomer, N′‐[7‐(acetyl‐4‐aminoanilino)‐9,9‐dioctylflouren‐2‐yl]‐N′‐4‐aminophenyl) acetamide (ADOAc), with flourene‐based structure was prepared from the reaction of 4‐aminoacetanillide with 2,7‐dibromo‐9,9‐dioctylfluorene in the presence of 10 mol % CuI, 20 mol % N,N′‐dimethylethylene diamine as catalyst and K₂CO₃ as base. Two new flourene‐ring containing polyimides were prepared from the reaction of ADOAc with aromatic dianhydrides such as pyromellitic dianhydride (PMDA) and 3,3′,4,4′‐benzophenonetetracarboxylic dianhydride (BTDA) via chemical imidization of poly(amic acid). The new diamine and the related polyimides were characterized by using conventional methods such as FT‐IR, NMR, and elemental analysis. The polyimides obtained from the reaction of ADOAc with PMDA (PIa) and of ADOAc with BTDA (PIb) had inherent viscosity of 0.49 and 0.58 dL/g respectively, and showed excellent solubility in a variety of organic solvents. The polyimides of PIa and PIb showed excellent thermal stability with 10% weight loss in nitrogen atmosphere at temperatures of 418°C and 407°C and T_g of 172°C and 167°C, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

长链聚酰亚胺的制备与表征

以长链二胺4,4' 二(4 氨基苯氧基)二苯砜(BAPS)为单体,采用两步法分别与二酐PMDA、ODPA、BPADA合成了3种链长的聚酰亚胺。实验利用GPC监测0 05mol/L聚酰胺酸(PAA)的数均聚合度(Xn)及相对分子质量分布随缩聚时间的变化关系,结果表明该反应为一逐步缩聚反应,缩聚速率随二酐电子亲和性(EA)的递增而增加;与预聚体聚酰胺酸相比,热处理环化得到聚酰亚胺其数均分子质量( Mn)和特性粘度[η]均有所下降,而分布指数(D)增大。此外还利用红外光谱(FTIR)、差分扫描量热法(DSC)、热重分析(TGA)等对聚酰亚胺进行了表征,结果表明聚酰亚胺(PI)的玻璃化温度(tg)和热分解温度(td)随着聚合单元长度的增加而降低。     

Annealing effect upon chain orientation, crystalline morphology, and polarizability of ultra-thin P(VDF-TrFE) film for nonvolatile polymer memory device

The ferroelectric behavior of spin-cast ultra-thin P(VDF-TrFE) (72-28) film is highly influenced by sample preparation methods including thermal annealing. The effect of sample preparation methods on the surface morphology, chain and dipole orientation, ferroelectric properties, and nonvolatile memory characteristics were studied using FTIR-grazing incident reflection absorption spectroscopy (GIRAS), grazing incident wide angle X-ray diffraction (GIWAXD), atomic force microscope (AFM), dynamic contact electrostatic force microscope (DC-EFM), and polarization-electric field (P-E) hysteresis measurements to find the feasibility of applying the ultra-thin P(VDF-TrFE) film to scanning probe microscopy (SPM)-based storage device or low-cost nonvolatile ferroelectric polymer random access memory (NvFePoRAM) device. From the collective analysis of GIRAS, GIWAXD, and AFM data, annealing the as-cast sample at temperature (ca. 120 °C) above Curie transition, but below its melting transition temperature was found to be the most suitable condition to fabricate the NvFePoRAM and/or SPM-based storage device with a memory density of about 30 GB/in². DC-EFM technique was successfully used to characterize the nonvolatile memory properties by ‘writing and erasing’ the data bit through applying a dc bias voltage much larger than coercive voltage with different polarities and then reading the data bit by applying a high frequency ac voltage of only 2 V to the ‘written or erased’ area.     

Excellent resistive memory characteristics and switching mechanism using a Ti nanolayer at the Cu/TaOx interface

Excellent resistive switching memory characteristics were demonstrated for an Al/Cu/Ti/TaO_x/W structure with a Ti nanolayer at the Cu/TaO_x interface under low voltage operation of ± 1.5 V and a range of current compliances (CCs) from 0.1 to 500 μA. Oxygen accumulation at the Ti nanolayer and formation of a defective high-κ TaO_x film were confirmed by high-resolution transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photo-electron spectroscopy. The resistive switching memory characteristics of the Al/Cu/Ti/TaO_x/W structure, such as HRS/LRS (approximately 10⁴), stable switching cycle stability (>10⁶) and multi-level operation, were improved compared with those of Al/Cu/TaO_x/W devices. These results were attributed to the control of Cu migration/dissolution by the insertion of a Ti nanolayer at the Cu/TaO_x interface. In contrast, CuO_x formation at the Cu/TaO_x interface was observed in an Al/Cu/TaO_x/W structure, which hindered dissolution of the Cu filament and resulted in a small resistance ratio of approximately 10 at a CC of 500 μA. A high charge-trapping density of 6.9 × 10¹⁶ /cm² was observed in the Al/Cu/Ti/TaO_x/W structure from capacitance-voltage hysteresis characteristics, indicating the migration of Cu ions through defect sites. The switching mechanism was successfully explained for structures with and without the Ti nanolayer. By using a new approach, the nanoscale diameter of Cu filament decreased from 10.4 to 0.17 nm as the CC decreased from 500 to 0.1 μA, resulting in a large memory size of 7.6 T to 28 Pbit/sq in. Extrapolated 10-year data retention of the Ti nanolayer device was also obtained. The findings of this study will not only improve resistive switching memory performance but also aid future design of nanoscale nonvolatile memory.     

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 of highly transparent and heat‐resistant polyimides containing bulky pendant moieties

A new diamine with bulky pendant biphenyl and ortho‐position dimethyl structures, 4,4′‐((1,1′‐biphenyl)‐4‐ylmethylene)bis(2,6‐dimethylaniline), was synthesized via a one‐pot reaction of 4‐biphenyl carboxaldehyde and 2,6‐dimethylaniline. The diamine was employed to polymerize with several dianhydrides via one‐step condensation under high‐temperature conditions. The light yellow or colorless polyimide (PI) films obtained were found to have cut‐off wavelengths in the range 286–358 nm and transmittance over 80% in the visible region (400–780 nm). Meanwhile, these PIs possessed excellent solubility in common organic solvents, even in low‐boiling‐point solvents such as chloroform (CHCl₃), dichloromethane (CH₂Cl₂) and tetrahydrofuran. The glass transition temperatures (T_g) of the PIs were determined to exceed 343 °C, even to 456 °C. All PI films were flexible with a tensile strength of 78–119 MPa, a Young's modulus of 2.0–2.5 GPa and elongation at break of 4.0%–8.2%. Therefore, these colorless PIs can be used as candidate materials for flexible display substrates. © 2019 Society of Chemical Industry     

Synthesis and properties of novel soluble polyimides having a spirobisindane-linked dianhydride unit

A new synthetic procedure was elaborated allowing the preparation of semiaromatic dianhydride. N-Methyl protected 4-chlorophthalic anhydride was nitrated with HNO₃ to produce N-methyl-4-chloro-5-nitrophthalimide (1). The aromatic nucleophilic substitution reaction between 5,5′,6,6′-tetrahydroxy-3,3,3′,3′-tetramethyl-1,1-spirobisindane and 1 afforded spirobisindane-linked bis(N-methylphthalimide) (2), which was hydrolyzed and subsequently dehydrated to give the corresponding dianhydride (3). The latter was polymerized with five different aromatic diamines to afford a series of aromatic polyimides. The properties of polyimides such as inherent viscosity, solubility, UV transparency and thermal stability were investigated to illustrate the contribution of the introduction of spirobisindane groups into the polyimide backbone. The resulting polyimides were readily soluble in polar solvents such as chloroform, THF and N-methyl-2-pyrrolidone. The glass-transition temperatures of these polyimides were in the range of 254-292 °C. The tensile strength, elongation at break, and Young's modulus of the polyimide film were 68.8-106.6 MPa, 5.9-9.8%, 1.7-2.0 GPa, respectively. The polymer films were colorless and transparent with the absorption cutoff wavelength at 286-308 nm.