1,3,5-三（4-二苯胺基苯乙炔基）-2,4,6-三（4-腈基苯乙炔基）苯的合成及表征

利用微波反应合成了一种新型二阶非线性光学化合物1,3,5-三（4-二苯胺基苯乙炔基）-2,4,6-三（4-腈基苯乙炔基）苯,通过红外、核磁共振、元素分析等手段对产物结构进行了表征。紫外可见光的吸收光谱的研究表明,该产物有希望成为1064 nm激光的倍频材料。     

Synthesis of novel cross-linked s-triazine-containing poly(aryl ether)s nanoparticles for biological fluorescent labeling

A blue-fluorescence 2,4,6-tris(4-fluorophenyl)-1,3,5-triazine (TFPT) monomer was synthesized with high yield and high purity under mild reaction conditions. The TFPT, which had three active fluoric groups, was facilely incorporated into stable cross-linked fluorescent polymeric nanoparticles (FCPNs) via precipitation polymerization with 6-(4-hydroxyphenyl)pyridazin-3(2H)-one (HPZ). The FCPNs were highly dispersible in water and showed uniform size, intense blue fluorescence, and excellent biocompatibility, making them promising for live cell imaging label applications. This work has the potential to promote the exploitation of novel s-triazine monomers, and to provide a new view of functional crossing-linked polymers based on such monomers.     

耐高温含氟聚芳醚酮和聚芳醚砜的合成与性能研究

通过三步反应合成新的含氟双酚单体3,4-二氟苯基对苯二酚,由该含氟双酚单体、4-氟苯基对苯二酚、邻苯基对苯二酚分别与4,4′-二氟二苯酮、4,4′-二氯二苯砜经亲核缩聚反应,制备了一系列新型聚芳醚酮和聚芳醚砜。采用 FT-IR、DSC、TGA及XRD手段等对聚合物的结构和性能进行了表征和研究,结果表明：合成的聚芳醚酮和聚芳醚砜具有优异的耐热性能,玻璃化转变温度分别在150~159 ℃和177~196 ℃之间,氮气中5 %热失重温度分别在527 ℃和507 ℃以上。合成的聚芳醚酮和聚芳醚砜具有良好的溶解性,室温下能溶解在N-甲基吡咯烷酮、二甲基乙酰胺、氯仿等有机溶剂中。     

Antioxidants and stabilizers. L. Transformation of the 1,3,5-tris(4-hydroxy-3,5-di-tert-butylbenzyl)cyanuric acid into alkylperoxycyclohexadienones,their properties and effects on the oxidation of tetralin and polypropylene

The transformation of 1,3,5-tris(4-hydroxy-3,5-di-tert-butylbenzyl)cyanuric acid (I), designed as an antioxidant for polyolefins, during its reaction with tert-butylperoxyls was studied. In tert-butyl alcohol two oxidation products, II and III, are formed, while in benzene the reaction proceeds faster with formation of cyclohexadienone III. The structures of the oxidation products were confirmed, their thermal properties were measured (by DTA) and the effect on the oxidation of tetralin and isotactic polypropylene was determined. The oxidative transformation makes trisphenol I lose its antioxidative property. The different behaviour of trisphenol I and another important phenolic antioxidant, namely, 1,3,5-trimethyl-2,4,6-tris(4-hydroxy-3,5-di-tert-butylbenzyl)benzene (IV) under the conditions of inhibited oxidation of polyolefins is discussed.     

Electronic properties of 1,3,5-tris[4-morpholinophenyl]benzene: a new molecular switch

A new electron-donor, 1,3,5-tris[4-morpholinophenyl]benzene 1, was synthetised via nickel-catalysed arylamination reactions and characterised by cyclic voltammetry. It was found that electrochemical or chemical oxidation of 1 generates mono- or di(cation radical)s that are stable over 30 min at room temperature.     

Cyclic ureas as solvents for poly(aryl ether) synthesis

Summary The synthesis of various poly(aryl ethers) and related small molecule compounds were examined using the cyclic urea 1,3-Dimethyl-3,4,5,6-tetrahydro-2(IH)-pyrimidinone (N,N′-dimethylpropylene urea, DMPU) as the solvent. The results showed that generally higher molecular weight or yields were obtained under less stringent conditions, as compared to other common polymerization solvents. The enhancement was most notable for polymerizations involving aryl fluorides with a lower reactivity than conventionally activated dihalide monomers, e.g. ketones, sulfones. Poly(aryl ethers) displayed excellent solubility in DMPU, which was beneficial in the cases where more rigid heterocyclic-aryl ether polymers are formed.     

Counteranion-directed assembly of zinc(II) coordination polymers with 1,3,5-tris(1-imidazolyl)benzene

Two novel coordination polymers [Zn₂(tib)(chda)Cl₂] (1) and [Zn(tib)I]I (2) have been prepared by reactions of 1,3,5-tris(1-imidazolyl)benzene (tib) and 1,2-cyclohexanedicarboxylic acid (H₂chda) with corresponding Zn(II) salts, respectively. Complex 1 has a three-dimensional (3D) structure with rare gra (graphite) topology, while 2 is a typical two-dimensional (2D) (4·8²) network. The results revealed that the counteranion plays a subtle and important role in the assembly procedure. Photoluminescent property of the complexes was investigated.     

新型聚芳醚砜共聚物的制备及其性能

以4,4’-二氯二苯砜、4,4’-二羟基二苯砜和2,4-二羟基二苯砜为单体,通过缩聚合成一系列主链含异构体醚键单元的聚芳醚砜共聚物,利用核磁共振碳谱(13C NMR)、差示扫描量热分析(DSC)和高压毛细管流变仪对产物进行了测试和分析。对比不同产物的熔体黏度、玻璃化转变温度和力学性能,发现随着共聚单元含量的增加,聚芳醚砜共聚物的流动性逐渐提高,玻璃化转变温度逐渐降低,并且屈服点伸长率和缺口冲击强度均逐渐提高。这一结果对实际应用中提高聚芳醚砜树脂流动性和韧性、降低热加工温度等具有重要的指导意义。     

Synthesis and properties of poly(aryl ether sulfone)s containing the phthalazinone moiety

Three series of poly(aryl ether sulfone)s (PAESs) containing the phthalazinone moiety in the polymer backbone were synthesized by solution polycondensation of bis(4-chlorophenyl) sulfone with three commercial bisphenols and 4-(4-hydroxyphenyl)-2,3-phthalazin-1-one. Bisphenol-A, hydroquinone, and bis(4-hydroxyphenyl) sulfone, or bisphenol-S, were selected as the commercial bisphenols for copolymerization. The synthesized polymers exhibited very high glass transition temperatures and excellent thermooxidative properties. They also showed superior mechanical properties and fair rheological properties. The introduction of relatively flexible moieties, such as benzene rings, onto the poly(phthalazinone ether sulfone) (PPES) chain led to a decrease in glass transition temperature with respect to the phthalazinone homopolymer. However, the processability of PPES was improved dramatically by the addition of these commercial bisphenols. The properties of synthesized PAESs can be tailored by changing the molar ratios of bisphenols to phthalazinone monomer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:137–143, 1998     

Evaluation of catalytic efficiency of a triple-site phase transfer catalyst and the kinetics of dichlorocarbene addition to 5-vinyl-2-norbornene

A new triple-site phase transfer catalyst viz., 1,3,5-tris(ethylmethyleneammonium bromide)-2,4,6-trimethyl benzene (TEMABTB) was prepared by the quaternization of 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene using triethylamine and its catalytic efficiency was ascertained by following the kinetics of dichlorocarbene addition of 5-vinyl-2-norbornene. Comparative catalytic activity of various onium salts (single-, di- and tri-site) have been investigated in detail. Based on the kinetic results obtained, a plausible mechanism has been proposed.     

5-对羧基苯基-10,15,20-三间羟基苯基二氢卟吩-PEG-叶酸的设计与合成

以聚乙二醇二胺、叶酸、5-对羧基苯基-10,15,20-三间羟基苯基二氢卟吩为原料,合成了2个光敏化合物:5-对羧基苯基-10,15,20-三间羟基苯基二氢卟吩-PEG-叶酸(3a)和5-对羧基苯基-10,15,20-三间羟基苯基二氢卟吩-PEG-NHBoc(3b),其结构经UV、IR、HPLC、1H MNR和MS确认。采用L9(33)正交实验法优化目标物3a的合成条件,在n(DCC)∶n(卟吩)=2∶1、反应温度为50℃、反应时间为5d时,3a收率最好。     

Antioxidants and stabilizers. IL. 1,3,5-trimethyl-2,4,6-tris (1-tert-butylperoxy-3,5-ditert-butylcyclohexa-2,5-diene-4-onylmethyl)benzene: Formation,properties and effect on the oxidation of tetralin and isotactic polypropylene

The transformation of the antioxidant 1,3,5-trimethyl-2,4,6-tris(3,5-ditert-butyl-4-hydroxybenzyl)benzene (I) by the oxidation with tert-butyl hydroperoxide in the presence of Co(II)acetylacetonate was investigated. The reaction in tert-butyl alcohol gives rise to product II of partial oxidation, while in benzene cyclohexadienone III is formed. The oxidation products were defined, and their thermal properties and behaviour in light were determined. The oxidative transformation of trisphenol I leads to a loss of its antioxidative activity. The oxidation products II and III at the temperature of their formation do not exhibit an unfavourable effect on the process of thermal oxidation. However, after heating of the hydrocarbon substrate containing them to a temperature close to their decomposition point they act as initiators. They undergo photochemical transformation already at room temperature and give colour to the polymer.     

Poly(aryl imino sulfone)s as new high-performance engineering plastics

Abstract  

Poly(aryl imino sulfone)s (PAISs) as novel high-performance polymers have been obtained by the condensation polymerization of 4,4′-dibromodiphenyl sulfone with different primary aromatic diamines via Palladium-catalyzed aryl amination reaction. The influence of the halogen-containing monomers, solvent, concentration, and temperature on the polycondensation reaction was investigated. The structure of polymers synthesized was characterized by means of FT–IR, NMR spectroscopy, and elemental analysis, the results showed an agreement with the proposed structure. Differential scanning calorimetry and thermal analysis measurements showed that polymers possessed high glass transition temperature (T _g > 145 °C) and good thermal stability with high decomposition temperatures (T _D > 450 °C). These novel polymers also exhibited good mechanical behaviors and good solubility.     

Crystal structure and photo-induced property of two-dimensional silver(I) complex with 1,3,5-tris(benzylsulfanyl)benzene

The silver(I) complex [Ag₂(3bsb)₂(ClO₄)₂] (1) (3bsb; 1,3,5-tris(benzylsulfanyl)benzene) has been prepared and its molecular structure was determined by X-ray crystallography. In 1, the silver ion prefers a tetrahedral coordination geometry and produces a two-dimensional sheet structure containing dimeric units. Irradiation of this complex 1 with light changes its color from white to pink; heat or exposure to acetone vapor makes the irradiated sample revert back to white. However, only 3bsb has no characteristic like this photochromism.     

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     

A novel photoactive hyperbranched poly(aryl ether ketone) with azobenzene end groups for optical storage applications

A novel hyperbranched poly(aryl ether ketone) terminated by azobenzene chromophores (azo-HPAEK) was prepared using 1,3,5-tris[4-(4-fluorobenzoyl)phenoxy] benzene (B₃) as a core molecule, 4,4′-(hexafluoroisopropylidene) diphenol as an A₂ monomer and 4-(4-hydroxyphenylazo) benzonitrile as an end-capping reagent. It is shown that azo-HPAEK exhibits a high glass transition temperature (Tg), excellent thermal stability and homogeneous photochromic behavior. By exposing the spin-coated film to a laser beam interference pattern, azo-HPAEK can be used for rapid (within 30 s) fabrication of surface relief gratings (SRGs), and the azo-HPAEK gratings cannot be totally erased by heating, even at 300 °C. In particular, azo-HPAEK shows a large photoinduced birefringence intensity and good reversible optical storage upon irradiation with 532 nm Nd:YAG laser.     

Preparation,spectroscopic, and electrochemical properties of four novel trinuclear Ru(II) polypyridyl complexes containing diazafluorene

Four tripodal ligands 2,2′,2″-tris[4-(4,5-diazafluoren-9-ylhydrazinyl)methylenephenoxyethyl]amine (L¹), 1,1,1-tris[4-(4,5-diazafluoren-9-ylhydrazinyl)methylenephenoxymethyl]propane (L²), 1,3,5-tris[4-(4,5-diazafluoren-9-ylhydrazinyl)methylenephenoxymethyl]-2,4,6-trimethylbenzene (L³), 1,3,5-tris[4-(4,5-diazafluoren-9-ylhydrazinyl)methylenephenoxymethyl]benzene (L⁴), and corresponding Ru(II) complexes [(bpy)₆L^1–4(Ru^II)₃](PF₆)₆ (Ru-L^1–4) have been synthesized. Cyclic voltammetry of these complexes comprise one Ru(II)-centered reversible oxidation and three ligand-centered reductions. Photophysical behaviors are investigated by UV–Vis absorption and luminescence spectrometry. These complexes display metal-to-ligand charge transfer absorption at around 410 nm and emission at around 582 nm.     

Electrochemical disproportionation in new ruthenium (II) nitro complexes with 2,4,6-tris(2-pyridyl)-1,3,5-triazine detected by IR spectroelectrochemistry with an OTTLE cell

The syntheses and characterization of new nitro complexes of Ru(II) with 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) and different substituted bipyridines are reported. A disproportionation reaction can occur after applying an oxidation potential corresponding to the couple Ru^II/Ru^III forming the nitrate and the nitrosyl complexes, which were detected by cyclic voltammetry. This reaction was confirmed by IR-spectroelectrochemistry with an OTTLE cell, for the first time. Additionally, for 2,2′-bipyridine we have obtained as ClO₄⁻ salt a new nitrosyl-complex which presents an elevated IR stretching frequency.     

Glass-forming 1,3-bis(carbazol-9-yl)propan-2-ol based monomers and polymers

Three glass-forming 1,3-bis(carbazol-9-yl)propan-2-ol based monomers, i.e. oxirane, thiirane and oxetane were synthesized. Photopolymerization of their solid amorphous layers initiated with diphenyliodonium tetrafluoroborate and the dark polymerization in solutions initiated with boron trifluoride etherate were performed. The number-average molecular weights of the obtained polymers are in the range of 1000-19,400. The highest initial polymerization rate, the highest limit conversion and the highest molecular weight were observed for the polymerization of thiirane. Optical, photophysical, electrochemical and thermal properties of the synthesized compounds were studied. UV and fluorescence spectra of the compounds have the similar profiles, due to the presence of the same chromophore. No excimer emission was observed neither for dilute solutions of monomers nor polymers. The electrochemical coupling was observed for all the synthesized 1,3-bis(carbazol-9-yl)propan-2-ol based monomers and polymers by cyclic voltammetry. The thermal degradation of the derivatives of 1,3-bis(carbazol-9-yl)propan-2-ol derivatives starts in the range of the temperatures from 317 to 402. The glass transition temperatures of the monomers range from 43 to 58 while glass transition temperatures of the polymers are in the range of 103-125.     

Synthesis of new poly(aryl ether)s with pendent benzoxazole groups via Ullmann ether reaction

A study has been done on the synthesis of new poly(aryl ether)s with two pendent benzoxazole groups via Ullmann condensation reaction. As a new rigid monomer, 1,4-bis(2-benzoxazolyl)-2,5-dibromobenzene ( II ) was synthesized in a two-step reaction starting from 2,5-dibromo-p-xylene. A model reaction of aryl dibromide II with two equivalents of m-cresol under Ullmann reaction conditions gave very high yield of the substitution product III , suggesting the possibility of producing polyethers in this system. The aryl dibromide monomer was polymerized with two different bisphenols (bisphenol A (BPA) and 4,4'-(hexafluoroisopropylidine)diphenol (BPA-6F)) in NMP or benzophenone/pyridine via CuCl-catalysed Ullmann reaction. The molecular weights of the obtained polymers ( IV ), however, seemed relatively low according to their solution viscosity. The resulting polymers showed good solubility in many common solvents including chlorinated hydrocarbons, tetrahydrofuran, pyridine as well as typical aprotic polar solvents. The glass transition temperatures were found at 168°C ( IV-a ) and 172°C ( IV-b ), respectively, and no melting transition appeared, indicating the amorphous nature of these polymers. The polymers were stable up to 400 – 450°C as determined by the weight loss onset temperature observed by TGA.