芳香族超支化聚酯的合成

以1,2,4-偏苯三酸酐、二元醇和一元醇为反应单体,采用溶液法和熔融法合成了具有芳香型结构的超支化聚酯.合成产物采用红外、核磁、GPC、粘度等进行了表征,并详细研究了反应条件对合成产物结构的影响.     

New Polymer Syntheses Part 53. Novel Polyamides of Diarylidenecycloalkanone Containing Azo Groups in the Polymer Backbone: Synthesis and Characterization

A new interesting class of polyamides of diarylidenecycloalkanone containing azo groups in the polymer backbone 6 _a-d was synthesized by a solution polycondensation reaction of bis 2-aminoarylidene monomers 3 _a,b with 4,4′-azodibenzoyl dichlorides and 3,3′-azodibenzoyl dichlorides in NMP as a solvent, using anhydrous LiCl as a catalyst at room temperature. The model compounds 4, 5 were synthesized by the interaction of one mole of bis 2-aminoarylidene monomers 3 _a,b with two moles of benzoyl chloride using anhydrous LiCl as a catalyst in NMP at room temperature. The resulting polymers were characterized by elemental and spectral analyses, besides solubility and viscometry measurements. The thermal properties of those polymers were evaluated by TGA, DTG and DTA measurements and correlated to their structural units. X–ray analysis of the polymers showed that polyamides based on para-azo linkage have a higher degree of crystallinity than those based on meta-azo linkage in the region 2θ = 5?60°. In addition, the morphological properties of selected examples were tested by SEM.      

Neo-Pentyl-Ferrocene Based Electroactive Polyesters

A series of polyesters with regularly spaced pendant ferrocenyl groups have been prepared from neo-pentylenediol and aromatic dicarboxylic acid precursors using a mild carbodiimide coupling protocol. A design feature of these polyesters is the regular spacing of the ferrocenyl unit, one per repeat unit, through the polymer chains. The covalently attached ferrocenyl groups can be oxidised chemically or electrochemically. The acyl or methyl linkers through which the ferrocenyl group is attached to the neo-pentylenediol component tune the redox properties of the polymers.     

Antimicrobial activity of some new 4‐arylazo‐3‐methylthiophene disperse dyes on polyester fabrics

A series of novel 4‐arylazo‐3‐methylthiophenes was synthesized by the heterocyclization of 2‐arylhydrazono‐2‐acetyl thioacetanilide derivatives with a variety of α‐halogenated reagents, such as chloroacetone, phenacyl bromide, ethyl chloroacetate, and chloroacetonitrile. The structures of the synthesized thiophene derivatives were confirmed by ultraviolet–visible, IR, and ¹H‐NMR spectroscopic techniques and elemental analysis. The synthesized dyes were applied to polyester fabrics as disperse dyes, and their fastness properties were evaluated. The dyed polyester fabrics displayed antibacterial efficacy against Gram‐positive (Staphylococcus aureus) and Gram‐negative (Escherichia coli) bacteria. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and Reactions of Organometallic Polymers Containing Titanacyclobutene Units in the Main Chain

A new class of polymers containing titanacyclobutene units in the main chain were prepared by the reaction of organic dihalides (2) with a binuclear titanium propargyl complex (3) generated in situ from bis(pentamethylcyclopentadienyl)titanium chloride (Cp*₂TiCl, 1), SmI₂, and 1,4-bis(3-bromopropynyl)benzene (2a). The dark red colored polymers (4) thus obtained are soluble in organic solvents such as tetrahydrofuran and chloroform, and they are stable at ambient temperature under argon atmosphere. The reaction of the titanium-containing polymers (4) with hydrogen chloride was found to give organic polymers (7) containing unsaturated main chain.     

Organometallic Derivatives of Polyphosphazenes as Precursors for Metallic Nanostructured Materials

Co-polyphosphazenes containing anchored organometallic fragments are useful precursors for nanostructured metallic materials. Pyrolysis in air at 800°C yields metallic nanoparticles of the type, M°/M _x O _y /M _z (P _x O _y )/P₄O₇, depending on the metal used; i.e., M° when the metal is a noble metal, metal oxide when the metal is Cr, W and Ru, metallic pyrophosphate when M = Mn and Fe. The organic spacer of the polyphosphazene influences strongly the morphology of the pyrolytic product. The mechanism of formation of the nanostructured materials involves carbonization of the organic matter, which produces holes where the nanoparticles are grown. Reaction of the phosphorus polymeric chain with O₂ yield phosphorus oxide units, which act as a P₄O₇ matrix to stabilize the nanoparticles and/or P _x O _y ⁻ⁿ for the formation of metallic pyrophosphates. The method appears to be a general and versatile new route to metallic nanostructured materials. Dedicated to Professor Harry Allcock for his pioneering and persevering work on Polyphosphazene and their projection in another field as materials and recently nanomaterials.     

Pressure‐Sensitive Chromogenic Polyesters

Cyano‐OPV moieties were covalently incorporated into a PETG backbone to create ductile amorphous polymers which change their PL and absorption color as a function of deformation. The cyano‐OPV concentration was systematically varied, and the composition was related to the material's optical response. This approach afforded PETG/dye copolymers which upon annealing display characteristics of aggregated dye molecules. The materials exhibit a significant color change upon compression, consistent with disassembly of the dye aggregates. This mechanochromic response is irreversible and can be detected by the unassisted eye.

     

非诱变偶氮染料的研究进展(I)──偶氮染料诱变性研究方法及其致癌机理

主要讨论了偶氮染料诱变性能研究方法及其致癌机理。偶氮染料诱变性能研究方法多采用“Ａｍｅｓ／Ｓａｌｍｏｎｅｌｌａ”测试法,而其致癌机理,目前大多数专家认为主要是通过它在动物（或人）体内偶氮还原开裂形成的芳胺或其相关化合物特别是芳氮烯阳离子来实现的。     

Poly(arylazophosphonates): New Arylazophosphonate‐Containing Polyurethanes and Polyesters for Laser Ablation Structuring

In this article we report the preparation of new arylazophosphonate‐containing polymers, poly(arylazophosphonates), via polycondensation reactions of bifunctional hydroxy functionalized arylazophosphonate‐containing monomers with isocyanate or acid chloride comonomers. The polyurethanes and polyesters were characterized by common methods such as ¹H, ¹³C, ³¹P NMR, FTIR, UV/visible spectroscopy, DSC, and GPC measurements. In addition, a number of polymer structuring experiments (macro and micro experiments) by means of laser ablation with a XeCl excimer laser were performed. In macro experiments, pulse number and fluence were investigated systematically and their influence on the ablation depth was discovered. In micro experiments, structures of high quality were obtained which possess clear contours without any debris on the polymer surface. Structures in the sub micron range were created by applying a phase mask. These high quality results indicate that the poly(arylazophosphonates) are well suited materials for laser ablation structuring with XeCl excimer lasers (e.g. for microstructuring or microlithography).

SEM image of sub micro structures of polymer APU 5 generated in experiments using a phase mask (line width: 0.3–0.5 μm, trench width: 0.3–0.5 μm, fluence: 3 J/cm²).     

Some New Organometallic Polyamides based on Ferrocene

Three new polyamides containing ferrocene units in the main chain were synthesized via low temperature polycondensation route, reacting 1,1′-ferrocenedicarboxylic acid chloride with three different types of aromatic diamines. The products were characterized by their solubilities, elemental analysis, FTIR spectral analysis, differential scanning calorimetry, thermogravimetry and viscosity measurements. The glass transition temperatures of the polymers were found by DSC curves and the activation energies of pyrolysis were estimated from TG curves applying Horowitz and Metzger method. Among these, polyamide P-1 (prepared from 4-(4-aminophenyloxy)phenyl-4-aminobenzamide) was found soluble in some of the organic solvents at room temperature but has poor thermal stability. Polyamide P-2 (prepared from 1,2-di(para-aminophenyloxy)ethylene) was soluble on heating and is thermally stable. However, all of these were also miscible with concentrated H₂SO₄ forming red coloured solutions.

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Graphical Abstract Ferrocenedicarbonyl chloride was reacted with three different types of aromatic diamines via solution polycondensation to get three new polyamides. Two of which were soluble in some organic solvents. The resulting polymers were characterized by their solubilities, viscosity measurements, elemental analysis, FTIR spectroscopy, differential scanning calorimetric and thermogravimetric studies.

     

Gas Barrier and Thermal Behavior of Long Chain Aliphatic Polyesters after Stressed Treatments

Poly(hexane dodecanoate)-based random copolyesters containing ether linkages have been subjected to contact with food simulant liquids and thermal and photoageing. Gas permeability, thermal and mechanical properties have been analyzed after each treatment, and the results obtained have been compared with low-density polyethylene films. The results showed that the gas barrier behavior was highly influenced by the polymer chemical composition. The contact with simulant liquids and the ageing treatments induced an increase in the crystallinity degree, together with a decrease in the molecular weight. This caused an increment of the elastic modulus and a decrement of the elongation at break.     

Green Synthesis of Novel Class of Azo Dyes Based on Naphthols,Coumarins, and Phenols with Molybdate Sulfuric Acid

A new series of polycyclic aromatic azo dyes based on naphthols, coumarins, and phenols were efficiently synthesized by the diazotization of 7-amino coumarins in the presence of catalytic amounts of molybdate sulfuric acid (MSA) followed by coupling reactions. The diazotization and subsequent azo-coupling generated the related azo dyes at 0–5°C in short reaction times with a simple experimental procedure.     

H-酸型偶氮染料光氧化脱色反应的QSPR研究

使用草酸铁／H2O2作为脱色剂对12种H-酸型偶氮染料进行光助氧化脱色反应，通过选择分子结构描述符和线性回归分析的方法对染料脱色反应半衰期T1／2及其分子结构进行了QSPR研究研究结果表明．对于所涉及的12种水溶性阴离子H-酸型偶氮染料，大多数染料的半衰期都在2～4分钟的范围内，分子结构描述符MW／S对半衰期的贡献最为显著，而芳香环数目和偶氯基数目对半衰期的贡献则不显著而对于典型H-酸型偶氯染料，其分子结构和脱色性能之间存在着更好的定量关系．三个分子结构描述符都成为对半衰期贡献的显著影响因素。     

偶氮液晶化合物的研究进展

偶氮液晶化合物是一类非常重要的功能材料。在光和热的作用下,偶氮液晶化合物会出现顺反异构现象。该类化合物既有光色效应,又有光致双折射效应,因此,偶氮液晶化合物不仅在信息材料领域具有潜在的应用前景,而且还是制备分子开关器件的首选对象。综述了近年来常见偶氮液晶化合物的发展概况,并概述了该类化合物的分类。     

双羟乙氨基-硝基型偶氮生色分子的二阶非线性极化率

设计并合成了6种具有D-π-A型和D-π-A-π-D型共轭结构的双羟乙氨基给体-硝基受体型偶氮化合物,用溶致变色法测算了分子的二阶非线性极化率。实验结果表明,双羟乙氨基和硝基是一对有效的给体、受体组合,它们与偶氮共轭链相连组成的分子具有较大的二阶非线性极化率,其中,具有D-π-A-π-D二维共轭结构的化合物,它包含两条从给体到受体的共轭链,二阶非线性极化率β1 064达到297.4×10(-30)esu,并且这个分子的透明性在6个分子中也是最好的,光学损耗最小。     

Cross‐Linking of Polyesters Based on Fatty Acids

This study aims at obtaining cross‐linked polymeric materials of biomass origin. For this purpose, one‐pot polyesterification of methyl ricinoleate and methyl 12‐hydroxystearate using titanium isopropoxide as a catalyst is performed leading to polyesters known as estolides. The obtained estolides are successfully cross‐linked using dicumyl peroxide or a sulfur vulcanization system. The so‐formed bio‐based elastomers appear to exhibit promising properties. The latter are analyzed by mechanical tensile tests and thermal techniques (TGA, DSC, DMA) and show high thermal stability (T_5% = 205–318 °C), tailored physico‐mechanical properties (low glass transition temperature in the range from ?69 to ?54 °C), and good tensile strength (0.11–0.40 MPa). Networks prepared from high molecular weight estolides appear to be promising bio‐based elastomers. Practical Applications: The vegetable oil‐based estolides described in this contribution are new fully bio‐based precursors for further elastomers synthesis. The resulting estolide networks (obtained by peroxide or sulfur cross‐linking) exhibit tailored thermo‐mechanical properties.     

线性PBS基脂肪族聚酯的合成和降解研究

为了探讨线性PBS基脂肪族共聚酯的结构和降解之间的关系,首先合成了线性PBS基脂肪族共聚酯,即聚丁二酸丁二醇酯-共-聚己二酸丁二醇酯P(BS-co-BA),聚丁二酸丁二醇酯-共-癸二酸丁二醇酯P(BS-co-BSe),并将线性PBS基脂肪族共聚酯及PBS在土壤悬浮液中进行降解,通过GPC、熔点测定仪对线性PBS基脂肪族共聚酯的分子量和熔点进行了测定;通过测定降解过程中失重率和降解前后聚酯薄膜表面形貌来对共聚酯降解程度进行表征。结果表明:随着二元酸碳链的增长,分子对称性降低,降解性能增大。通过观察分子量,熔点及降解失重率的测定结果,得出分子量越大,降解越不容易进行;熔点越小,降解性能越好。     

偶氮染料废水处理研究现状及其发展方向

从物理法、化学法、生化法三方面概述了对偶氮染料废水处理的研究现状 ,同时给偶氮染料废水的处理提供了一些参考意见。     

润滑剂TAF对聚酯流变性能的影响

在常规涤纶 ( PET)和阳离子可染涤纶 ( CDPET)中加入润滑剂 TA F,考察了共混物的流变性能 ,发现加入 TAF后 PET和 CDPET的表观粘度明显下降。用 DSC测定了共混物的玻璃化温度 Tg和熔点 Tm,共混物的 Tg和 Tm 均没有变化