Synthesis and characterization of new thermally stable poly(ester‐imide)s derived from 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl and various aromatic dihydroxy compounds

A series of new alternating aromatic poly(ester‐imide)s were prepared by the polycondensation of the preformed imide ring‐containing diacids, 2,2′‐bis(4‐trimellitimidophenoxy)biphenyl (2a) and 2,2′‐bis(4‐trimellitimidophenoxy)‐1,1′‐binaphthyl (2b) with various aromatic dihydroxy compounds in the presence of pyridine and lithium chloride. A model compound (3) was also prepared by the reaction of 2b with phenol, its synthesis permitting an optimization of polymerization conditions. Poly(ester‐imides) were fully characterized by FTIR, UV‐vis and NMR spectroscopy. Both biphenylene‐ and binaphthylene‐based poly(ester‐imide)s exhibited excellent solubility in common organic solvents such as tetrahydrofuran, m‐cresol, pyridine and dichloromethane. However, binaphthylene‐based poly(ester‐imide)s were more soluble than those of biphenylene‐based polymers in highly polar organic solvents, including N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, N,N‐dimethylformamide and dimethyl sulfoxide. From differential scanning calorimetry thermograms, the polymers showed glass‐transition temperatures between 261 and 315 °C. Thermal behaviour of the polymers obtained was characterized by thermogravimetric analysis, and the 10 % weight loss temperatures of the poly(ester‐imide)s was in the range 449–491 °C in nitrogen. Furthermore, crystallinity of the polymers was estimated by means of wide‐angle X‐ray diffraction. The resultant poly(ester‐imide)s exhibited nearly an amorphous nature, except poly(ester‐imide)s derived from hydroquinone and 4,4′‐dihydroxybiphenyl. In general, polymers containing binaphthyl units showed higher thermal stability but lower crystallinity than polymers containing biphenyl units. Copyright © 2005 Society of Chemical Industry     

Gel formation in diimide‐hydrogenated polymers

The hydrogenation of diene‐based polymers via diimide is a very attractive alternative to the conventional catalytic hydrogenation route based on gaseous molecular hydrogen. However, serious crosslinking always accompanies it and limits the end‐use properties of the polymers. Gel formation in polymers that are hydrogenated via diimide has been investigated in detail through an inspection of all the chemical reactions involved in the process. The results indicate that hydrogen peroxide decomposition, some reactions related to oxygen, and the redox reaction between hydrogen peroxide and hydrazine are capable of generating radicals. However, radicals generated in the aqueous phase do not appear to initiate the crosslinking of diene‐based polymers in the latex form. It is proposed that the primary radicals giving rise to crosslinking are generated in the polymer phase in situ, and the step responsible for generating these organic radicals is possibly the diimide disproportionation reaction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1122–1125, 2005     

Bulky rigid substitutions: A route to high electron mobility and high solid-state luminescence efficiency of perylene diimide

In this paper, we report that a kind of perylene diimide derivative with bulky rigid substituents, 1,7-bis(p-tert-butylphenoxy)-N,N′-dicyclohexyl-perylene-3,4,9,10-tetracarboxylic diimide (TBPCHPDI) possesses both high electron mobility (1.8 cm² V⁻¹s⁻¹) and high fluorescence quantum yield (0.32) in the solid state. Through X-ray diffraction (XRD), UV–Vis absorption and fluorescence spectra, and differential scanning calorimetry (DSC) measurements, it is demonstrated that the above phenomenon can be ascribed to the unique crystal structure of TBPCHPDI: due to steric hindrance of bulky rigid substituents, the intermolecular π–π actions are neglectable, providing high luminescence efficiency; in the mean time, the spacing between perylene chromophores is still very short (3.47 Å), which is favorable for the hopping transportation of charge carrier from one molecule to neighboring molecule. Therefore, our finding would help design and synthesize novel organic semiconductive materials with potential applications in electrically pumped lasers which require high emission efficiency when large current density is applied.     

The mutual influence of surface energy and substrate temperature on the saturation mobility in organic semiconductors

We report on a mutual correlation between the substrate temperature during semiconductor deposition and the surface energy of the gate dielectric on the charge carrier mobility in bottom gate top contact organic field effect transistors (OFETs) with N,N′-diphenyl-3,4,9,10-perylene tetracarboxylic diimide (DP-PDI) as organic semiconductor.     

Polylactide‐perylene derivative for blue biodegradable organic light‐emitting diodes

In this work we demonstrate, for the first time, the use of polylactic acid (PLA) as a biodegradable host matrix for the construction of the active emissive layer of organic light‐emitting diode (OLED) devices for potential use in bioelectronics. In this preliminary study, we report a robust synthesis of two fluorescent PLA derivatives, pyrene‐PLA ( AH10 ) and perylene‐PLA ( AH11 ). These materials were prepared by the ring opening polymerisation of l ‐lactide with hydroxyalkyl‐pyrene and hydroxyalkyl‐perylene derivatives using 1,8‐diazabicyclo[5.4.0]undec‐7‐ene as catalyst. OLEDs were fabricated from these materials using a simple device architecture involving a solution‐processed single‐emitting layer in the configuration ITO/PEDOT:PSS/PVK:OXD‐7 (35%): AH10 or AH11 (20%)/TPBi/LiF/Al (ITO, indium tin oxide; PEDOT:PSS, poly(3,4‐ethylenedioxythiophene) doped with poly(styrenesulfonic acid); PVK, poly(vinylcarbazole); OXD‐7, (1,3‐phenylene)‐bis‐[5‐(4‐tert‐butylphenyl)‐1,3,4‐oxadiazole]; TPBi, 2,2′,2″‐(1,3,5‐benzenetriyl)tris(1‐phenyl‐1H‐benzimidazole)). The turn‐on voltage for the perylene OLED at 10 cd m^–2 was around 6 V with a maximum brightness of 1200 cd m^–2 at 13 V. The corresponding external quantum efficiency and device current efficiency were 1.5% and 2.8 cd A^–1 respectively. In summary, this study provides proof of principle that OLEDs can be constructed from PLA, a readily available and renewable bio‐source. © 2020 The Authors. Polymer International published by John Wiley & Sons Ltd on behalf of Society of Industrial Chemistry.     

逐层组装多层膜对苝的固相萃取性能研究

利用聚电解质逐层自组装技术在氨基硅胶表面构筑聚(乙烯-alt-马来酸)的苯乙胺衍生物(PEMAPEA)/聚烯丙基胺盐酸盐(PAH)多层膜,制备性能稳定的新型固相萃取吸附材料。利用HPLC-UV/Vis检测,研究其对水体中苝的萃取性能,考察柱填料量、样品量、上样流速、洗脱溶剂等对多层膜萃取性能的影响。结果表明:含150 mg固相萃取填料的3 mL萃取小柱,以10 mL·min-1的流速萃取200 mL苝的水溶液,用丙酮作洗脱剂,萃取回收率达到90%以上。     

Highly soluble perylene dyes: Synthesis, photophysical and electrochemical characterizations

Highly soluble perylene diimide derivatives with symmetrical and unsymmetrical secondary, tertiary alkyl side chains were synthesized and their photophysical properties, redox potentials and thermal stabilities were measured and compared with previously reported 1-pentylhexyl substituted swallow-tailed perylene diimide. Diasteroisomers of the novel, unsymmetrical swallow-tailed substituted perylene diimide compound could not be detected using low temperature NMR spectroscopy. The novel dyes were soluble in a range of organic solvents indicating potential for photo-electronic applications and photocatalytic reactions. Two dyes were not only soluble in organic solvents but also showed solubility in aqueous media as the hydrochloride salt, thus offering potential use in biological applications.