Novel poly(amide‐hydrazide)s and copoly(amide‐hydrazide)s from bis‐(4‐aminobenzyl) hydrazide and aromatic diacid chlorides: Synthesis and characterization

A new aromatic diamine, viz., bis‐(4‐aminobenzyl) hydrazide (BABH), which contains preformed hydrazide and methylene linkage, was synthesized starting from α‐tolunitrile. The BABH and intermediates involved in its synthesis were characterized by spectroscopic methods. Novel poly(amide‐hydrazide)s were synthesized by low temperature solution polycondensation of BABH with isophthaloyl chloride (IPC) and terephthaloyl chloride (TPC). Furthermore, two series of copoly(amide‐hydrazide)s, based on different mol % of BABH and bis‐(4‐aminophenyl) ether (ODA) with IPC/TPC were also synthesized. Poly(amide‐hydrazide)s and copoly(amide‐hydrazide)s were characterized by inherent viscosity [η_inh], FTIR, solubility, X‐ray diffraction (XRD), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The polycondensation proceeded smoothly and afforded the polymers with inherent viscosities in the range of 0.18–0.93 dL/g in (NMP + 4% LiCl) at 30°C ± 0.1°C. These polymers dissolved in DMAc, NMP or DMSO containing LiCl. The solubility of copolymers was considerably improved in line with less crystalline nature due to random placement of constituent monomers during the copolymerization. XRD data indicated that poly(amide‐hydrazide)s from BABH alone and IPC/TPC had higher crystallinity than the corresponding copoly(amide‐hydrazide)s derived from a mixture of BABH and bis‐(4‐aminophenyl) ether (ODA). Polymers showed initial weight loss around 160°C which is attributed to the cyclodehydration leading to the formation of corresponding poly(amide‐oxadiazole)s. Copolyamide‐hydrazides showed T_max between 400 and 540°C which is essentially the decomposition of poly(amide‐oxadiazole)s. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of poly(arylene ether sulfone)s with pendant amines on the main chain

Summary Synthesis of poly(arylene ether sulfone)s with random incorporation of pendant aryl amines was achieved by copolymerization of dichlorodiphenylsulfone (DCDPS) and bisphenol-A with bis(4-fluorophenyl)-3-aminophenylphosphine oxide (amino DFTPPO) with N-methylpyrrolidone (NMP) as the solvent, toluene as the azeotrope and potassium carbonate (K₂CO₃) as the weak base. A unique feature of this polymerization is that one of the comonomer (amino DFTPPO) contains both an amine functionality as well as activated dihalides which can undergo aromatic nucleophilic displacement by the phenolate, the degree of amination on the main chain can be controlled very precisely by regulating the amount of the amino DFTPPO monomer relative to the other activated dihalide monomer (DCDPS) and bisphenol-A. The synthesis and characterization of poly(arylene ether sulfone)s with various concentration of amine groups on the backbone will be discussed in this paper.     

Synthesis and curing behavior of macrocycle‐terminated poly(aryl ether ketone)s

BACKGROUND: The introduction of poly(ether ether ketone)‐based carbon‐fiber composites accelerated the application of poly(ether ether ketone)s in advanced composite materials. In order to improve the compatibility and processability with reinforced components, polymers with low melt viscosity are preferable. RESULTS: Novel fully aromatic macrocycle‐terminated poly(aryl ether ketone)s (MCPAEKs) were prepared by condensation of macrocyclic aryl ether ketone dimers containing hydroxyphenyl groups and fluorine end‐capped poly(aryl ether ketone) oligomers. Compared with liner poly(aryl ether ketone)s, MCPAEKs showed much lower melt viscosities at low temperature. In the presence of caesium fluoride, the crosslinking reaction of MCPAEKs afforded fully aromatic thermoset poly(aryl ether ketone)s by ring‐opening reaction. CONCLUSION: The MCPAEKs exhibited high thermal stability due to their wholly aromatic structures. After crosslinking, the glass transition temperatures and complex melt viscosities of the polymers were increased greatly. Although there was some residual cesium fluoride or phenoxides produced by ring‐opening reaction, the thermoset poly(aryl ether ketone)s obtained had good thermal stability with temperatures at 5% weight loss above 475 °C. Copyright © 2009 Society of Chemical Industry     

化学交联胍基功能化阴离子交换膜的制备

化学交联改性是提高阴离子交换膜机械性能的有效方法。采用有机强碱五甲基胍（PMG）作为功能化试剂,对氟化聚芳醚噁二唑（FPAEO）进行了功能化反应,加入六氟双酚A（6F-BPA）进行化学交联改性处理制得交联型氟化聚芳醚噁二唑阴离子交换膜(FPAEO-AEMs)。分析结果表明：交联剂6F-BPA为6%时,溶胀率为28.8%;吸水率为86.27%;电导率达到3.12×10^-2 S·cm^-1;离子交换容量（IEC）为2.57 mequiv·g^-1;热分解温度可达280℃。     

Precipitation polymerization of acrylamide with quaternary ammonium cationic monomer in potassium carbonate solution initiated by plasma

Precipitation polymerization of 2‐(methacryloyloxyethyl) trimethyl ammonium chloride (DMC)‐co‐acrylamide (AM) [poly(AM‐DMC)] has been successfully performed in potassium carbonate (K₂CO₃)‐water media by plasma initiation. K₂CO₃ solution was selected because not only the higher solubility of AM and DMC comparing with that of poly(AM‐DMC), but the higher intrinsic viscosity of poly(AM‐DMC) could be obtained. A set of experiments was performed using different K₂CO₃ concentration (from 50 down to 10% (w/w)), thus the precipitation architecture was not obtained below 20% (w/w). And particles size, particles size distribution (7–120 μm), and intrinsic viscosity of poly(AM‐DMC) (ranging up to 455 cm³/g) were also summarized in this article. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4060–4067, 2007     

New poly(1,3,4‐oxadiazole)s bearing pentadecyl side chains: Synthesis and characterization

The 4‐[4′‐(Hydrazinocarbonyl)phenoxy]‐2‐pentadecylbenzohydrazide was polycondensed with aromatic diacid chlorides viz., terephthalic acid chloride (TPC), isophthalic acid chloride (IPC), and a mixture of TPC : IPC (50 : 50 mol %) to obtain polyhydrazides which on subsequent cyclodehydration reaction in the presence of phosphoryl chloride yielded new poly(1,3,4‐oxadiazole)s bearing flexibilizing ether linkages and pentadecyl side chains. Inherent viscosities of polyhydrazides and poly(1,3,4‐oxadiazole)s were in the range 0.53–0.66 dL g^?1 and 0.49–0.53 dL g^?1, respectively, indicating formation of medium to reasonably high molecular weight polymers. The number average molecular weights (M_n) and polydispersities (M_w/M_n) of poly(1,3,4‐oxadiazole)s were in the range 14,660–21,370 and 2.2–2.5, respectively. Polyhydrazides and poly(1,3,4‐oxadiazole)s were soluble in polar aprotic solvents such as N,N‐dimethylacetamide, 1‐methyl‐2‐pyrrolidinone, and N,N‐dimethylformamide. Furthermore, poly(1,3,4‐oxadiazole)s were also found to be soluble in solvents such as chloroform, dichloromethane, tetrahydrofuran, pyridine, and m‐cresol. Transparent, flexible, and tough films of polyhydrazides and poly(1,3,4‐oxadiazole)s could be cast from N,N‐dimethylacetamide and chloroform solutions, respectively. Both polyhydrazides and poly(1,3,4‐oxadiazole)s were amorphous in nature and formation of layered structure was observed due to packing of pentadecyl chains. A decrease in glass transition temperature was observed both in polyhydrazides (143–166°C) and poly(1,3,4‐oxadiazole)s (90–102°C) which could be ascribed to “internal plasticization” effect of pentadecyl chains. The T₁₀ values, obtained from TG curves, for poly(1,3,4‐oxadiazole)s were in the range of 433–449°C indicating their good thermal stability. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci 124:1281–1289, 2012     

Silicone as an organosilicon reagent for the palladium-catalyzed cross-coupling reaction

Silicone, poly(diorganosiloxane), serves as an organosilicon reagent for palladium-catalyzed cross-coupling reactions. Treatment of poly[(aryl)methylsiloxane], poly[(alkenyl)methylsiloxane], or cyclic oligosiloxanes with various aryl iodides in the presence of silver(I) oxide (Ag₂O) or tetrabutylammonium fluoride (TBAF) and a catalytic amount of palladium affords the corresponding cross-coupling product in a good to excellent yield. The reaction of silicone with aryl chlorides in the presence of K₂CO₃/H₂O as an activator proceeded to afford biaryl derivatives in moderate to excellent yields. A wide range of aryl chlorides bearing an electron-donating or electron-withdrawing substituent on the aromatic ring are tolerated.     

Synthesis of a novel poly(aryl ether) with pendent N-phenylimide groups

A novel monomer with two N-phenylimide activating groups for the preparation of poly(aryl ether)s was investigated. A poly(aryl ether) was prepared by nucleophilic halide displacement from an aromatic dihalide monomer containing two N-phenylimide groups by sodium salts of bisphenol A. The monomers and the resulting polymer were characterized by FT-IR and ¹H NMR spectroscopy, elemental analysis and differential scanning calorimetry (DSC). The prepared polymer with a molecular weight of 6 300 and a polydispersity of 1.37 determined by GPC is readily soluble in polar aprotic solvents, e. g. dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP). Despite the low molecular weight the polymer is thermally stable up to 390°C and has a glass transition temperature of 218°C which is identical to that of ULTEM® poly(ether imide).     

Synthesis and properties of poly(aryl ether ketone ketone)/poly(aryl ether ether ketone ketone) copolymers with pendant cyano groups

2,6‐Diphenoxybenzonitrile (DPOBN) was synthesized by reaction of phenol with 2,6‐difluorobenzonitrile in N‐methyl‐2‐pyrrolidone in the presence of KOH and K₂CO₃. Poly(aryl ether ketone ketone)/poly(aryl ether ether ketone ketone) copolymers with pendant cyano groups were prepared by the Friedel–Crafts electrophilic substitution reaction of terephthaloyl chloride with varying mole proportions of diphenyl ether and DPOBN using 1,2‐dichloroethane as solvent and N‐methyl‐2‐pyrrolidone as Lewis base in the presence of anhydrous AlCl₃. The resulting polymers were characterized by various analytical techniques, such as FT‐IR, differential scanning calorimeter, thermal gravimetric analysis, and wide‐angle X‐ray diffraction. The crystallinity and melting temperature of the polymers were found to decrease with increase in concentration of the DPOBN units in the polymer. Thermogravimetric studies showed that all the polymers were stable up to 514°C in N₂ atmosphere. The glass transition temperature was found to increase with increase in concentration of the DPOBN units in the polymer when the molar ratios of DPOBN to DPE ranged from 10/90 to 30/70. The copolymers containing 30–40 mol % of the DPOBN units exhibit excellent thermostability at (350 ± 10)°C and have good resistance to acidity, alkali, and organic solvents. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3601–3606, 2007     

Facile synthesis and characterization of hyperbranched poly(aryl ether ketone)s obtained via an A2 + BB′2 approach

A fast and highly efficient approach for the synthesis of hyperbranched poly(aryl ether ketone)s (HPAEKs) via the polycondensation of A₂ and BB′₂ monomers is described. Commercially available hydroquinone (HQ, A₂ monomer) and easily synthesized 2,4′,6‐trifluorobenzophenone (TF, BB′₂ monomer) were thermally polycondensed to prepared fluoro‐ or phenolic‐terminated HPAEKs with K₂CO₃ and Na₂CO₃ as catalysts. During the reaction, the fluorine at the 4′‐position of TF reacts rapidly with the phenolic group of HQ, forming predominantly dimers and some other species. The dimer can be considered as a new AB′₂ monomer. Further reactions among molecules AB′₂ and AB′₂ with some other species result in the formation of HPAEKs. Fourier transform infrared and ¹H NMR spectra revealed the structures of the resultant polymers. The degree of branching (DB) of the fluoro‐terminated hyperbranched polymers was determined to be in the range 50–57% from ¹H NMR spectra, whereas the DB of the phenolic‐terminated hyperbranched polymers was determined to be 100%. These hyperbranched polymers exhibit excellent solubility in general organic solvents and possess moderate molecular weights with broad distributions determined using gel permeation chromatography. Moreover, the structure and performance of the HPAEKs can be conveniently regulated by adjusting the type and feed ratio of the two monomers. Copyright © 2010 Society of Chemical Industry     

Synthesis and evaluation of properties of poly(p‐phenylenevinylene) based 1,3,4‐oxadiazole systems for optoelectronics and nonlinear optical applications

Two new π‐conjugated polymers, namely poly(p‐phenylenevinylene‐1,3,4‐oxadiazole) (PPVO) and poly(p‐(nitro‐phenylene)vinylene‐1,3,4‐oxadiazole) (PNPVO), were synthesized and characterized. The Gilch polymerization technique, using dihalo derivatives of 1,3,4‐oxadiazoles, was employed to synthesize them under mild reaction conditions. The macromolecules exhibit good solubility in dimethylformamide, formamide and dimethyl sulfoxide and thus effectively address the insolubility issues associated with many oxadiazole derivatives for device fabrication. They show bright luminescence in the blue‐green region of the electromagnetic spectrum and have optical band gaps suited for an emissive layer in organic light‐emitting devices. PPVO and PNPPO show good non‐linear optical responses also in solution phase, with third‐order nonlinear susceptibilities of the order of 10^?12esu. Interestingly, they exhibit good antimicrobial characteristics under examination with Escherichia coli and Staphylococcus. The results prove that these macromolecules are ideal materials to use as emissive layers in various light‐emitting devices and NLO applications. The excellent antimicrobial activity can be utilized for their applications in clinical and healthcare areas. © 2016 Society of Chemical Industry     

Microwave promoted synthesis and characterization of isomeric poly(ether ether ketone)s

A series of isomeric poly(ether ether ketone)s were synthesized using microwave‐assisted method by nucleophilic substitution reaction of hydroquinone and 4,4′‐biphenol with 4,4′‐difluorobenzophenone (DFBP) or 2,4′‐DFBP in the presence of anhydrous K₂CO₃. The polymers with inherent viscosities in the range of 0.20–0.71 dlg^?1 were obtained in quantitative yields and had excellent thermal stability as shown by the temperature of 5% weight loss in nitrogen above 410°C. X‐ray diffraction patterns confirmed the semicrystalline character of some of the polymers. The results also indicate that the reaction time was shortened remarkably and the reaction temperature could be controlled easily. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Synthesis and characterization of poly(aryl ether ketone) oligomers terminated with metallophthalocyanine to be used for oxidative decomposition of TCP

A series of metallophthalocyanine‐terminated poly(aryl ether ketone) oligomers were synthesized from dicyanobenzene‐terminated poly(aryl ether ketone) oligomers with different metal chloride and phthalonitrile. All polymers exhibited high glass transition temperature and good thermal stability. These polymers showed optical absorption in the visible region and had different colors in chloroform solution. Cobalt phthalocyanine‐terminated poly(aryl ether ketone) oligomers exhibited good catalytic activity in oxidative decomposition of 2,4,6‐trichlorophenol (TCP) under H₂O₂ and KHSO₅. The catalytic activity of KHSO₅ is much better than H₂O₂, and more than 70% of initial TCP was decomposed within 7 h. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Dendron-functionalized perylene diimides with carrier-transporting ability for red luminescent materials

This paper presents a series of dendrimers via a convergent synthetic approach with three generations, which contain perylene diimide cores, Fréchet-type poly(aryl ether) dendrons, and carbazole (CZ) or oxadiazole (OXZ) peripheral functional groups. The higher generation dendrimer has an obvious site-isolation or dilution effect of dendrons, which results in a relatively small red-shift of absorption and emission spectra when it forms a solid thin film for applications. The interactions between peripheral units and perylene diimide core in the dendrimers are also studied by steady-state and time-resolved fluorescence spectra under both direct and indirect excitation. The fluorescence data show that there exist two possible mechanisms, Förster energy transfer (FRET) and photo-induced electron transfer (PET), for dendrimers bearing carbazole units. No enhanced core fluorescence is observed because the energy transfer or light-harvesting potential of peripheral carbazole is counteracted by PET. While for dendrimers bearing oxadiazole units, no PET can take place between OXZ and perylene diimide since both of them are high electron affinity. The FRET and higher light-harvesting ability of oxadiazole without PET interfering result in the distinct enhancement of core emission in higher generation dendrimers. DSC results indicate that the incorporation of Fréchet-type poly(aryl ether) dendrons can improve the amorphous property and increase glass transition temperature (T_g). The preliminary EL results with single-layer architectures demonstrate that these dendrimers could be utilized as a promising kind of active red luminescent emitters with carrier-transporting ability. EL emission has the same recombination zone as PL, indicating that the recombination of excitons in fabricated EL devices is not close to cathode or anode vicinity. It is suggested that the site-isolation effect of dendron wedges is attributed to prevent the core luminorphores from approaching electrodes efficiently.     

Synthesis of poly[methyl(phenyl)silanediyl] containing 1,3,4-oxadiazole electron-transporting moieties

Summary The new oxadiazole derivative containing amino group, 2-(4-aminophenyl)-5-(biphenyl-4-y1)- 1,3,4-oxadiazole (Oxad-NH₂), was synthesized and attached to formylated poly[methyl(phenyl)silanediyl] (PMPSi) by acid-catalyzed condensation of the aldehyde with the amino group yielding a Schiff base. The aldehyde groups were incorporated into the parent PMPSi by the reaction with dichloromethyl methyl ether in the presence of Lewis acid (SnCl₄). GPC analyses before and after modification reaction revealed that the attachment of Oxad-NH₂ proceeded without degradation of the silicon backbone. We reached 75 % conversion of aldehyde groups to oxadiazole Schiff base. The condensation reaction was followed and the prepared compounds and polymers were characterized by ¹H NMR, UV-vis, FT IR, GPC and elemental analyses. Fluorescence behavior of oxadiazole-modified PMPSi was studied in tetrahydrofuran. Broad emission band with maximum at 440 nm was observed. Fluorescence quantum yield of modified polysilanes increases with the increasing content of the attached oxadiazole moiety. Received: 10 February 2003/Revised version: 8 April 2003/Accepted: 8 April 2003 Correspondence to Drahomír Vyprachticky     

Studies on the synthesis and properties of hydroxyl azacrown ether‐grafted chitosan

The chitosan hydroxyl azacrown ether was synthesized by reaction of hydroxyl azacrown ether with epoxy‐activated chitosan. The C₂ amino group in chitosan was protected from the reaction between benzaldehyde and chitosan to form N‐benzylidene chitosan. After reaction with epichlorohydrin and azacrown ether, reacting O‐aryl mesocyclic diamine‐N‐benzylidene chitosan and dilute ethanol hydrochloride solution to obtain novel chitosan‐azacrown ether bearing hydroxyl removed the Schiff base. Its structure was confirmed with elemental analysis, FTIR spectra analysis, X‐ray diffraction analysis, and solid‐state ¹³C NMR analysis. Its static adsorption properties for Ag(I), Cd(II), Pb(II), and Cr(III) were also investigated. The experimental results showed that the hydroxyl azacrown ether grafted chitosan has good adsorption capacity and high selectivity for Ag(I) in the coexistence of Pb(II) and Cd(II), the selectivity coefficients of hydroxyl azacrown ether chitosan were K_Ag(I)/Pb(II) = 32.34; K_Ag(I)/Cd(II) = 56.12. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1838–1843, 2001     

Synthesis and alkaline stability of novel cardo poly(aryl ether sulfone)s with pendent quaternary ammonium aliphatic side chains for anion exchange membranes

Novel cardo poly(aryl ether sulfone)s containing pendent -[CH₂CH₂NMe₃]⁺OH⁻, or -[CH₂CH₂CH₂NMe₃]⁺OH⁻ groups, and partially fluorinated cardo poly(aryl ether sulfone) containing pendent -[CH₂CH₂CH₂NMe₃]⁺OH⁻ groups were synthesized and examined with the focus of understanding how the polymer chemical structure affects their morphology, ion conductivity and alkaline stability. The resulting quaternized polymers exhibited outstanding solubility in polar aprotic solvents. The partially fluorinated cardo poly(aryl ether sulfone)s (PES-PF-OH) with ion-exchange capacity of 1.44 meq g⁻¹ displayed the highest ion conductivities, varied from 3.0 × 10⁻² to 4.1 × 10⁻² S cm⁻¹ over the range 20-60 °C. TEM revealed that PES-PF-OH membrane exhibited a distinct phase-separated morphology comprised of interconnected ionic clusters in size of 1-2 nm. The studies on alkaline stability of the membranes revealed that the PES-PF-OH polymer was not stable under strong basic conditions. The quarternized polymers containing pendent -[CH₂CH₂NMe₃]⁺OH⁻, or -[CH₂CH₂CH₂NMe₃]⁺OH⁻ groups mainly underwent Hofmann elimination and S_N2 substitution reaction.     

A comparative structure-property study of methylphenylated and fluoromethylphenylated poly(aryl ethers) and their gas permeabilities and permselectivities

Two novel poly(aryl ether)s, dimethylphenylated poly(ether nitrile) (6H-PEN) and dimethylphenylated poly(ether ether ketone) (6H-PEEK), derived from (3,5-dimethylphenyl)hydroquinone monomer, were synthesized via aromatic nucleophilic substitution polycondensation. They showed high glass transition temperatures and were soluble in common solvents. A comparison of gas permeabilities and permselectivities among methylphenylated (3H-PEEK and 3H-PEN), trifluoromethylphenylated (3F-PEEK and 3F-PEN), dimethylphenylated (6H-PEEK and 6H-PEN) and 3,5-ditrifluoromethylphenylated (6F-PEEK and 6F-PEN) poly(aryl ether)s were studied. Compared with the methylated polymers, the corresponding fluoromethylated polymers had generally higher permeabilities. The 3F and 6F polymers had combined permeabilities and permselectivity properties attractive for O₂/N₂ separation. 6F-PEN exhibited the best gas separation properties for the O₂/N₂ pair, and P(O₂), and P(O₂)/P(N₂) values were 6.6 and 5.9, respectively.     

2-芳基-5-氯甲基-1,3,4-(口恶)二唑的改进合成方法

芳酸与氯乙酰肼在二甲苯中用三氯氧磷作催化剂,一步高收率合成2-芳基-5-氯甲基-1,3,4-噁二唑。     

Photoinduzierte Zersetzung von Aryldiazoniumsalzen durch Metalloxalate

Photoinduced Decomposition of Arene Diazonium Salts by Metal Oxalates Arene diazonium salts were decomposed by the irradiation of K₃[Fe(oX)₃] and K₃ [Co(ox)₃]. The dediazonation is caused by electron transfer reactions between ·CO^-₂ and in the case of the former complex also by [Fe(ox)₂]^2- -species. As intermediates aryl radicals were found by spin trapping with nitroso durene. The dediazonation quantum yields (0,15--1,21) depend on the reduction potentials of the salts and on the oxalate concentration. By electron acceptor substituted diazonium salts the values are the same as those of the K₃[Fe(ox)₃]-actinometer. In the case of p-dialkylaminobenzene diazonium salt-types an electron transfer takes places with ·CO^-₂ only whereas the reaction with [Fe(ox)₂]²⁻ is neglectable. A Hammett-correlation for the electron transfer of Fe(II)-species with a ϱ-value of 1.7 was found. The investigated systems are efficient initiators of the photopolymerization.