Recombination luminescence of poly(arylene phthalide) films: 1. Electronic and optical features of poly(arylene phthalide)s

Features of the luminescence and absorption spectra of poly(biphenylene phthalide), poly(fluorenylene phthalide), and poly(terphenylene phthalide) films were analyzed. Experimental results obtained for these films by optical methods and thermally stimulated current spectroscopy were compared. Long-lasting afterglow emission from the films after photoexcitation was observed. Possible explanations for the observed optical and thermally stimulated processes in the poly(arylene phthalide)s were suggested in terms of reversible electronic phase transitions induced by external factors in unconjugated polymers.     

Copoly(arylene phthalides) in the thermal polymerization of styrene

Russian Chemical Bulletin - The thermal polymerization of styrene in the presence of polymer initiators, copoly(arylene phthalides) of the diphenyl oxide series with different ratios of two...     

PEP型嵌段共聚醚非离子表面活性剂的研究

以聚乙二醇和环氧丙烷为原料，用常压法合成了一系列氧丙烯—氧乙烯—氧丙烯嵌段共聚醚，对合成产物进行了结构表征，并对产物的浊点、泡沫稳定性、临界胶束浓度、乳化性能等进行了测定。研究结果表明，氧丙烯—氧乙烯—氧丙烯嵌段共聚醚作为非离子表面活性剂，其性能与嵌段序列长度和含量密切相关。     

Recombination luminescence of poly(arylene phthalide) films: 2. Afterglow emission induced by electric excitation in poly(arylene phthalide) films

Absorption, luminescence and electroluminescence spectra of films of the unconjugated copolymer poly(arylene ether ketone) (CPAEK) were measured. Long-lasting afterglow emission was observed resulting from electro- and photoexcitation of the CPAEK films. and is possible mechanisms of generation are discussed.     

Modification Pathways for Copoly(2‐oxazoline)s Enabling Their Application as Antireflective Coatings in Photolithography

Chromophore‐functionalized copoly(2‐oxazoline)s are successfully evaluated as bottom antireflective coatings (BARCs) in high‐resolution photolithography. With respect to UV light sources used in photolithographic production routines, anthracene is chosen as a chromophore. For application as polymer in BARCs, the copolymer poly(2‐ethyl‐2‐oxazolin)₄₅‐stat‐poly(2‐dec‐9′‐enyl‐2‐oxazolin)₂₀‐stat‐poly(2‐(3′‐(1″‐(anthracen‐9‐ylmethyl)‐1″,2″,3″‐triazol‐4‐yl)propyl)‐2‐oxazolin)₃₅ can be synthesized by the Huisgen cycloaddition click reaction of the copolymer poly(2‐ethyl‐2‐oxazolin)₄₅‐stat‐poly(2‐dec‐9′‐enyl‐2‐oxazolin)₂₀‐stat‐poly(2‐pent‐4′‐inyl‐2‐oxazolin)₃₅ and the corresponding azide‐functionalized anthracenes. These copolymers can be crosslinked by the thermally induced thiol‐ene reaction involving the unsaturated C=C bonds of the poly(2‐dec‐9′‐enyl‐2‐oxazoline) repetition units and a multifunctional thiol as crosslinker. Tests of this BARC in a clean room under production conditions reveal a significant decrease of the swing‐curve of a chemically amplified positive photoresist by more than 50%, hence significantly increasing the resolution of the photoresist.

     

Poly(arylene ether)s,poly(arylene thioether)s,and poly(arylene sulfone)s derived from a dihydroxy(imidoarylene) monomer

Novel poly(arylene ether)s, poly(arylene thioether)s, and poly(arylene sulfone)s were synthesized from the dihydroxy(imidoarylene) monomer 1 . The syntheses of poly(arylene ether)s were carried out in DMAc in the presence of anhydrous K₂CO₃ by a nucleophilic substitution reaction between the bisphenol and activated difluoro compounds. Poly(arylene thioether)s were synthesized according to the recently discovered one-pot polymerization reaction between a bis(N,N′-dimethyl-S-carbamate) and activated difluoro compounds in the presence of a mixture of Cs₂CO₃ and CaCO₃. The bis(N,N′-dimethyl-S-carbamate) 3 was synthesized by the thermal rearrangement reaction of bis(N,N′-dimethylthiocarbamate) 2 , which was synthesized from 1 by a phase-transfer catalyzed reaction. The poly(arylene thioether)s were further oxidized to form poly(arylene sulfone)s, which would be very difficult, if not impossible, to synthesize by other methods. All of the polymers described have extremely high T_gs and thermal stability as determined from DSC and TGA analysis. Poly(arylene sulfone)s have the highest T_gs and they are in the range of 298–361°C. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1201–1208, 1998     

Electroluminescence in unconjugated polymers based on poly(arylene phthalide) films

We discuss the results of measurements of the optical characteristics of thin organic films of unconjugated poly(arylene ether ketone) polymer. We have observed persistent electroluminescence for this polymer. We have established an interrelationship between the polarity of the voltage applied to the experimental structure and the electroluminescence spectrum. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 1, pp. 42–45, January–February, 2009.     

Recombination luminescence of poly(arylene phthalide) films induced by visible light

Long-term afterglow emission (AG) of poly(arylene phthalide) films (PAP) irradiated with visible light has been discovered. Recombination nature of the AG was experimentally proven as in the case of UV irradiation. Features of the observed AG spectra were analyzed in comparison with the photo-, electro-, and thermoluminescence spectra of the PAP films in relation to the commonness of the AG generation mechanism, which is associated with the involvement of the two-photon reactions and triplet states in the photoprocesses in PAP.     

Copoly(arylene ether nitrile) and copoly(arylene ether sulfone) ionomers with pendant sulfobenzoyl groups for proton conducting fuel cell membranes

Three series of fully aromatic ionomers with naphthalene moieties and pendant sulfobenzoyl side chains were prepared via K₂CO₃ mediated nucleophilic aromatic substitution reactions. The first series consisted of poly(arylene ether)s prepared by polycondensations of 2,6‐difluoro‐2′‐sulfobenzophenone (DFSBP) and 2,6‐dihydroxynaphthalene or 2,7‐dihydroxynaphthalene (2,7‐DHN). In the second series, copoly(arylene ether nitrile)s with different ion‐exchange capacities (IECs) were prepared by polycondensations of DFSBP, 2,6‐difluorobenzonitrile (DFBN), and 2,7‐DHN. In the third series, bis(4‐fluorophenyl)sulfone was used instead of DFBN to prepare copoly(arylene ether sulfone)s. Thus, all the ionomers had sulfonic acid units placed in stable positions close to the electron withdrawing ketone link of the side chains. Mechanically strong proton‐exchange membranes with IECs between 1.1 and 2.3 meq g⁻¹ were cast from dimethylsulfoxide solutions. High thermal stability was indicted by high degradation temperatures between 266 and 287 °C (1 °C min⁻¹ under air) and high glass transition temperatures between 245 and 306 °C, depending on the IEC. The copolymer membranes reached proton conductivities of 0.3 S cm⁻¹ under fully humidified conditions. At IECs above ∼1.6 meq g⁻¹, the copolymer membranes reached higher proton conductivities than Nafion^® in the range between −20 and 120 °C. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Voltammetric determination of bisoprolol on a glassy carbon electrode modified by poly(arylene phthalide)

New voltammetric sensors based on glassy carbon electrodes (GCEs) modified by poly(arylene phthalide) are studied. The electrochemical behavior of bisoprolol on GCEs modified by poly(arylene phthalide) is investigated. The effects of potential scan rate, time of accumulation on the electrode, pH of supporting electrolyte, and concentration on the current of bisoprolol electrooxidation are estimated. A procedure is developed for the voltammetric determination of bisoprolol on glassy carbon electrodes modified by poly(arylene phthalide). The dependence of the analytical signal on the concentration of bisoprolol is linear in the range 10^–6–10^–5 M with the limit of detection (3.4–9.8) × 10^–8 M.     

Control over the Composition and Microstructure of Copoly(Arylene Phthalides)

The possibility of controlling the composition, microstructure, and molecular weight of copoly(arylene phthalides) was examined.     

Ionic Liquids as Novel Reaction Media for the Synthesis of Copoly(ester-amide)s Containing 9,10-Anthraquinone Moiety

The use of ionic liquids as novel solvents for the synthesis of aromatic copoly(ester-amide)s, containing a 9,10-anthraquinone moiety in the main chain, from the polycondensation reaction of terephthaloyl chloride and various ratios of p-phenylenediamine and 1,4-dihydroxyanthraquinone is reported. 1,3-Dialkylimidazolium-based ionic liquids are suitable reaction media for the synthesis of copoly(ester-amide)s. These copolymers exhibit color characteristics and thermal stability. The presence of the amide groups in the backbone of these polymers enhances their thermal stabilities. Inherent viscosities of the polymers obtained in 1,3-dialkylimidazolium bromide range from 0.28 to 0.42 dL/g.     

Synthesis and properties of novel poly(arylene ether)s and poly(arylene thioether)s based on a pyridazine biphenol or a phthalazine biphenol

Novel sulfur‐containing biphenol monomers were prepared in high yields by the reaction of 4‐mercaptophenol with chloropyridazine or chlorophthalazine compounds. High‐molecular‐weight poly(arylene ether)s were synthesized by a nucleophilic substitution reaction between these sulfur‐containing monomers and activated difluoro aromatic compounds. The inherent viscosities of these polymers ranged from 0.34 to 0.93 dL/g. The poly(pyridazine)s exhibited glass‐transition temperatures greater than 165 °C. The poly(phthalazine)s showed higher glass‐transition temperatures than the poly(pyridazine)s. A polymer synthesized from a bisphthalazinebiphenol and bis(4‐fluorophenyl)sulfone had the highest glass‐transition temperature (240 °C). The thermal stabilities of the poly(pyridazine)s and poly(phthalazine)s showed similar patterns of decomposition, with no significant weight loss below 390 °C. The poly(phthalazine)s were soluble in chlorinated solvents such as chloroform, and the poly(pyridazine)s were soluble in dipolar aprotic solvents such as N,N′‐dimethylacetamide. The soluble poly(pyridazine)s and poly(phthalazine)s could be cast into flexible films from solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 262–268, 2007     

水溶性超支化共聚(酯-胺)的分子设计及合成

超支化聚酯是超支化聚合物中的一大类 [1～ 4 ] ,由于酯结构能在自然环境下降解 ,因而引起了许多研究者的兴趣 .Hult[1,5] ,Voit[6 ,7] 和 Kricheldorf等 [8] 在合成超支化聚酯方面做出了卓有成效的贡献 .他们用带羧基和羟基的 AB2 型单体在催化剂作用下缩合反应制得超支化聚酯 ;或先将羟基保护起来 ,再把羧基酰氯化 ,得到带酰氯的 AB2 型单体 ,经进一步缩聚得到超支化聚酯 .但用这种传统方法合成的超支化聚酯一般不溶于水 ,因而在某些领域的应用受到了限制 .本文提出了一种合成水溶性超支化聚酯的新策略 ,超支化聚酯并不是用酸与醇直接…     

Poly(arylene ether)s and poly(arylene thioether)s containing the 1,2-dihydro-4-phenyl(2H)- phthalazinone moiety

A series of new high molecular weight poly(arylene ether)s containing the 1,2-dihydro-4-phenyl(2H)phthalazinone moiety have been synthesized. The inherent viscosities of these polymers are in the range of 0.33–0.64 dL/g. They are amorphous and readily soluble in chloroform, DMF, and DMAc. The glass transition temperatures of the polymers range from 241 to 320°C and the 5% weight loss temperatures in nitrogen atmosphere range from 473 to 517°C. The hydroxy group in the monomer 1,2-dihydro-4-(4-hydroxyphenyl)(2H)phthalazin-1-one has been selectively transformed into the N,N′-dimethylthiocarbamate group, which was then rearranged to give the S-(N,N′-dimethylcarbamate) group via the Newman–Kwart rearrangement reaction. A series of poly(arylene thioether)s containing the 1,2-dihydro-4-phenyl(2H)phthalazinone moiety have also been synthesized via two types of reactions, a N C coupling reaction and a one-pot reaction between the S-(N,N′-dimethylcarbamate) and activated dihalo compounds, in diphenyl sulfone in the presence of a cesium carbonate and calcium carbonate mixture. These poly(arylene thioether)s also have high glass transition temperatures (ranging from 217–303°C) and high thermal stabilities. Compared with their poly(ether) analogs, the poly(arylene thioether)s have glass transition temperatures several degrees lower, which is attributed to the more flexible C S C bonds. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36 : 455–460, 1998     

Copoly(Aryl Ether)s Containing 1,10‐Phenanthroline Moieties

Abstract

Poly(aryl ether)s were synthesized by reaction of 4,7‐dichloro‐3,8‐diphenyl‐1,10‐phenanthroline and 4,7‐dichloro‐2,9‐dimethyl‐1,10‐phenanthroline with bisphenol A (BPA) in the presence of potassium carbonate in N,N‐dimethylacetamide or N‐methylpyrrolidinone. High molecular weight homopolymers could not be prepared because of the insolubility of the polymers resulting in premature precipitation from the reaction mixture. Soluble, high molecular weight copolymers were readily prepared containing up to 70 mol% of the 1,10‐phenanthroline moieties. The copolymers were all highly fluorescent with blue emission.     

Synthesis and characterization of soluble,fluorescent poly(arylene ether)s,poly(arylene thioether)s,and poly(arylene sulfone)s containing 1,3,5‐triphenylbenzene segments

The bisphenol 4,4″‐dihydroxy‐5′‐phenyl‐m‐terphenyl ( 4 ), containing a 1,3,5‐triphenylbenzene moiety, was synthesized from a pyrylium salt obtained by the reaction of benzaldehyde with p‐methoxyacetophenone with boron trifluoride etherate as a condensing agent. Polymers were obtained from 4 by a nucleophilic displacement reaction with various activated difluoro monomers and with K₂CO₃ as a base. A series of new poly(arylene ether)s ( 8a – 8f ) were obtained that contained phenyl‐substituted m‐terphenyl segments in the polymer chain. Polymers with inherent viscosities of 0.41–0.99 dL/g were obtained in yields greater than 96%. The polymers were soluble in a variety of organic solvents, including nonpolar solvents such as toluene. Clear, transparent, and flexible films cast from CHCl₃ showed high glass‐transition temperatures (T_g = 198–270 °C) and had excellent thermal stability, as shown by temperatures of 5% weight loss greater than 500 °C. 4 was converted via N,N‐dimethyl‐O‐thiocarbamate into the masked dithiol 4,4″‐bis(N,N′‐dimethyl‐S‐thiocarbamate)‐5′‐phenyl‐m‐terphenyl and was polymerized with activated difluoro compounds in the presence of a mixture of Cs₂CO₃ and CaCO₃ as a base in diphenyl sulfone as a solvent. A series of new poly(arylene thioether)s ( 9a – 9e ) were obtained with T_g values similar to those of 8a – 8e . 9a – 9e were further oxidized into poly(arylene sulfone)s with T_g values 40–80 °C higher than those for 8a – 8e and 9a – 9e . These polymers also had good solubility in organic solvents. A sulfonic acid group was selectively introduced onto the pendent phenyl group of polymers 8a and 8f by reaction with chlorosulfonic acid. The polymers were soluble in dipolar aprotic solvents and formed films via casting from dimethylformamide. Polymers 8a – 8f , 11a , and 11f showed blue and red fluorescence under ultraviolet–visible light with emission maxima at 380–440 nm. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 496–510, 2002; DOI 10.1002/pola.10136     

Phthalide as an activating group for the synthesis of poly(aryl ether phthalide)s by nucleophilic aromatic substitution

The phthalide ring was examined as an activating group for nucleophilic aromatic substitution. The proposed mechanism by which activation occurs is through a ring opening of the phthalide ring to form a Meisenheimer‐like σ complex. 3,3‐Bis(4‐fluorophenyl)phthalide was synthesized and examined under different reaction conditions to determine its suitability for polymer formation. Semiempirical calculations at the PM3 level suggested that 3,3‐bis(4‐fluorophenyl)phthalide is only moderately activated, whereas ¹H, ¹³C, and ¹⁹F NMR spectroscopy suggested that the monomer was not sufficiently activated for nucleophilic aromatic substitution. However, low‐molecular‐weight polymers (number‐average molecular weight < 7000 g/mol) were produced from bisphenol A, hydroquinone, and phenolphthalein. The polymers were characterized by gel permeation chromatography, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, NMR spectroscopy, and differential scanning calorimetry. The polymers displayed relatively high glass‐transition temperatures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3046–3054, 2002