New carbon-rich organometallic architectures based on cyclobutadienecyclopentadienylcobalt and ferrocene modules

This review describes the chemistry of alkynylated cyclobutadiene complexes and alkynylated ferrocenes. These complexes are made by a combination of metalation, formylation and Ohira alkynylation. The transformation of a formyl group into an alkyne is a critical step in these syntheses. The use of a diazophosphonate as the source of a carbon atom is convenient and has allowed for the synthesis of a host of alkynylated π-complexes. Multiply alkynylated ferrocenes and cyclobutadiene(cyclopentadienyl)cobalt complexes are utilized as stepping stone for complex carbon-rich organometallics. Half-wheel, butterfly, and similar structures have been accessed and characterized by single crystal X-ray methods. A ferrocene-fused dehydro[18]annulene decomposes explosively when heated above 200 °C with formation of carbon nanostructures that are bagel- or onion-shaped and that have been characterized by electron microscopy. This account as well describes the synthesis and characterization of organometallic dendrimers and conjugated organometallic polymers.     

Novel ferrocene modified poly(amide ether amide)s and investigation of physical and thermal properties

A new diamine containing ferrocene group with preformed ether and amide units was prepared via reaction of 1,1′-ferrocenedicarbonyl chloride with two moles of 2,6-bis(5-amino-1-naphthoxy)pyridine. Polycondensation reactions of the prepared diamine with different aromatic and aliphatic diacid chlorides in the presence of trimethylchlorosilane (TMSCl) resulted in preparation of novel ferrocene modified poly(amide ether amide)s. The monomer and polyamides were characterized and the effect of trimethylchlorosilane (TMSCl) as activating agent on the polymerization reaction was studied. The physical and thermal properties of the polyamides including inherent viscosity, solubility, thermal stability and behavior, flame-retardancy and crystallinity of the polymers were studied. The polymers showed good thermal stability and flame-retardancy, and also improved solubility in polar aprotic solvents.     

Synthesis and Characterization of Soluble Polyester Based on Calixarene Dicarboxylic Acid with Tertiary Butyl Pendant Groups

A series of new polycalixesters(PCES) were synthesized by polyesterification of calixarene dicarboxylic acid derivatives having tertiary butyl pendant groups at the upper rim using five different diols. All polyesters were readily soluble in polar solvents such as NMP(N-methylpyrrolidone), DMF(dimethylformamide), DMSO(dimethylsulfoxide), pyridine, THF(tetrahydrofurane), HMPA(hexamethylenephosphoramide) and DMAC(dimethylacetamide). The PCES were also partially soluble in TCE(tetrachloroethane) and ethanol and they were unsoluble in aceton. The glass transition temperatures of polyesters were between 80-184 °C, the crystallinity temperatures of polyesters were between 130–212 °C and the melting temperatures of polyesters were between 185–234 °C, as determined by differential scanning calorimeter(DSC). The inherent viscosities of polyesters were obtained from 0.55 dL/mg to 0.61 dL/mg. The temperatures at 10% weight loss of polyesters ranged from 182 °C to 237 °C. The temperatures at 25% weight loss of polyesters ranged from 258 °C to 331 °C. The half weight loss(50%) temperatures of polyesters were among 315 °C to 371 °C and the char yields at 600 °C were determined within 13% to 22.3% in N2 atmosphere, as determined by thermo gravimetric analysis(TGA). The polyester, PES3, has the higher melting point(234 °C) and higher inherent viscosity(molecular weight) than the other polyesters.     

Synthesis and properties of a novel polyester containing bithiazole

A novel Schiff base type polyester containing 2,2’-diamino-4,4’-bithiazole(DABT) was prepared by low-temperature interface polycondensation of 1,4-benzenedicarbonyl dichloride with 4,4’-(4,4’-bithiazole-2,2’-diylbis(imine-2,1-diyl)diphenol(BDDP), which is derived from a 2,2’-diamino-4,4’-bithiazole(DABT) Schiff base reacted with a 4-hydroxybenzaldehyde monomer.The newly generated polyester was evaluated based on characterization of its solubility,FTIR spectroscopy,elemental analysis,X-ray diffraction measurements and thermogravimetric analysis(TGA) studies.     

Structures and charge-discharge properties of spin-carrying ferrocene derivatives

Several ferrocene derivatives (1-6) carrying nitroxide radical were prepared as dual redox compounds. They have distorted molecular structures and exhibit oxidation potentials based on both ferrocene and nitroxide groups except 4. The multi-step charge-discharge processes are discriminated for mono-substituted derivatives with the first discharge capacity up to 400 Ah kg⁻¹ for imino-derivative 3, while relatively characterless profiles are observed for bis-substituted derivatives 4 and 6 with capacity over 300 Ah kg⁻¹.     

Synthesis of an anion receptor for acetate based on the frame of ferrocene

An anion receptor was synthesized with ferrocene as binding frame. Anion recognition can be monitored by anion complexation-induced changes in UV-vis absorption spectra. Interaction between the receptor and acetate was described on the basis of ¹H NMR experiments.     

Pyrolysis study of a phosphorus-containing aliphatic-aromatic polyester and its nanocomposites with layered silicates

This paper deals with the thermal decomposition behaviour of a new fire retardant 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-containing aliphatic-aromatic polyester and its nanocomposites with natural layered silicate (montmorillonite) under inert atmosphere studied by TGA-FTIR, Pyrolysis-GC/MS of volatile products and ATR-FTIR of non-volatile decomposition products. The phosphorus-containing polyester undergoes decomposition in two steps between 340 and 516 °C. The first step is associated with the release of carbon dioxide, acetaldehyde, ethene, acid-containing products (mainly benzoic acid) resulting in the formation of polyarylates followed by their decomposition in the second step with the evolution of carbon dioxide. DOPO-containing products, esters (mainly diethenyl terephthalate), carbon monoxide, acids and water are released through both stages. At the end of decomposition polyaromatic structures, diarylketones and organophosphorus esters built into the chemical structure of the char develop in the solid residue. The modification of the polyester with a layered silicate does not change the composition of the pyrolysis products, only their yield, and tended to diminish the charring of the polymer. A thermal decomposition scheme of the P-polyester is proposed and the mass spectra of some DOPO-containing products are discussed.     

Synthesis and application of some novel fluorescent heterocyclic disperse dyestuffs based on phenothiazine on polyester

A series of novel heterocyclic disperse dyestuffs derived from phenothiazine were prepared by standard reactions from phenothiazine as the starting material. Phenothiazine was nitrated and oxidized then reduced to obtain synthesized disperse dyestuffs. The reaction conditions were varied in order to obtain optimal yields for each stage of the preparation to obtain the corresponding derivative and final disperse dyestuffs. All intermediates and disperse dyestuffs were purified and characterized by DSC, FTIR, ¹H NMR, ¹³C NMR, elemental analysis and UV–Visible spectroscopic techniques. The molar extinction coefficients (ε), wavelengths of maximum absorption (λ_max) and solvatochromism effects were studied in solvents as toluene, acetone and N,N-dimethylformamide (DMF). Results represented that the dyestuffs had extinction coefficients of 2011–28189 L mol⁻¹ cm⁻¹, wavelengths of maximum absorption of 448–475 nm in acetone and positive solvatochromism by changing solvent from toluene to DMF. The disperse dyestuffs were applied to locally manufactured polyester fibers and their dyeing properties were investigated. Results showed that the buildup of dyestuffs was acceptable and dyed fibers had very good heat and wash fastness and medium light fastness on polyester fibers.     

Novel polyester/SiO2 nanocomposite membranes: Synthesis,properties and morphological studies

In this paper, a new type of soluble polyester/silica (PE/SiO₂) hybrid was prepared by the ultrasonic irradiation process. The coupling agent γ-glycidyloxypropyltrimethoxysilane (GOTMS) was chosen to enhance the compatibility between the polyester (PE) and silica (SiO₂). Furthermore, the effects of the coupling agent on the morphologies and properties of the PE/SiO₂ hybrids were investigated using UV-vis and FT-IR spectroscopies and FE-SEM. The densities and solubilities of the PE/SiO₂ hybrids were also measured. The results show that the size of the silica particle was markedly reduced by the introduction of the coupling agent, which made the PE/SiO₂ hybrid films become transparent. Furthermore, thermal stability, residual solvent in the membrane film and structural ruination of membranes were analyzed by thermal gravimetric analysis (TGA). The effects of SiO₂ nanoparticles on the glass transition temperature (T_g) of the prepared nanocomposites were studied by differential scanning calorimetry (DSC). Moreover, their mechanical properties were also characterized. It can be observed that the Young's moduli (E) of the hybrid films increase linearly with the silica content. The results obtained from gas permeation experiments with a constant pressure setup showed that adding SiO₂ nanoparticles to the polymeric membrane structure increased the permeability of the membranes.     

Planar chiral ferrocene salen-type ligands featuring additional central and axial chirality

We report on novel chiral tridentate [NO₂]H₂ and tetradentate [N₂O₂]H₂ Schiff base ligands containing a planar chiral ferrocene moiety linked to hydroxyl-imine or diimine donors with central or axial chirality. Structurally, these ligands resemble half-salen and salen systems designed for stereoselective applications of their transition metal complexes in homogeneous catalysis. The modular synthesis involves diastereoselective metalation of chiral ferrocene or pentamethylferrocene acetals, followed by stereoconservative hydroxyalkylation and condensation with chiral hydroxyamines or diamines, respectively. In comparison to salen-type systems, an important advantage of these ligands is their tunable steric protection of the alkoxide donor site. A total of 18 different ligands varying in electronic and steric properties have been prepared and fully characterized by NMR, IR, mass spectroscopy and by single crystal structure analysis of nine precursors and representatives.     

高分子立构复合结晶的研究进展

立构复合结晶是高分子结晶中的一种普遍现象,也是不同高分子之间共结晶的特殊形式.互为立体异构高分子在共混物和立体嵌段共聚物中可形成立构复合结晶.由于这种独特的链凝聚结构,立构复合结晶材料与相应的同质结晶材料的性能显著不同,立构复合结晶通常可提高高分子材料的熔点、耐热性、结晶能力、结晶度、机械力学性能、耐溶剂性能等.通过立构复合结晶,可使一些非晶或难结晶的高分子转变为可结晶或高结晶度的状态,从而实现材料性能的转变.因此,互为立体异构高分子之间的立构复合结晶为聚合物材料的性能优化和调控提供了有效的途径.文献已报道了多类可立构复合结晶的聚合物体系,包括脂肪族聚酯、脂肪族聚碳酸酯、聚甲基丙烯酸酯、聚酰胺和聚酮等.本文根据聚合物化学结构的不同,针对文献已报道的可立构复合结晶的高分子体系,综述了其立构复合结晶的形成条件、结构特征与物理性质.     

Synthesis and characterization of novel polyesters derived from 4-aryl-2,6-bis(4-chlorocarbonyl phenyl) pyridines and various aromatic diols

A new class of aromatic polyesters containing pyridine heterocyclic rings (PE_1-15) was prepared via reactions of 4-aryl-2,6-bis(4-chlorocarbonyl phenyl) pyridines (DAC_1-3) and commercial diols by high temperature solution polymerization method in o-dichlorobenzene and catalytic amount of triethylamine hydrochloride. The optimum condition of polymerization was obtained via study of a model compound prepared from reaction of 4-phenyl-2,6-bis(4-chlorocarbonylphenyl) pyridine (DAC₁) and phenol. All polymers were characterized by FTIR and ¹H-NMR spectroscopies, and their physical properties including solution viscosity, solubility properties, thermal stability and thermal behavior were studied. The prepared polyesters showed excellent thermal stability and good solubility in polar aprotic solvents.     

二茂铁不同取代基对其电化学行为的影响

基于二茂铁不同取代基的氧化还原性,利用玻碳电极研究二茂铁及其醇类、醛类、羧酸类的电化学性质。通过循环伏安法探讨了取代基诱导效应和共轭效应对二茂铁电化学性质的影响,并用计时安培法测定了上述8种化合物的扩散系数,探讨了取代基与参数的相关性。     

Surface modification of polyester fabric by corona discharge irradiation

Polyester fabric was treated by corona discharge irradiation at different voltages. The treated fabric showed increased wicking and hydrophilic properties and the properties can be preserved for a long time. Dyeing of the treated fabric showed that dyeing speed and the dye-uptake were improved. Surface affinity between the treated fabric surface with modified starch sizing was also confirmed to be increased. This is generally useful for the sizing of polyester staple yarn and the polyester fabric dyeing. All the results are supposed due to the improved hydrophilic properties produced by the corona discharge treatment.     

Novel soluble fluorinated aromatic polyamides derived from 2-(4-trifluoromethylphenoxy)terephthaloyl chloride with various aromatic diamines

A series of novel fluorinated aromatic polyamides derived from a new monomer, 2-(4-trifluoromethylphenoxy)terephthaloyl chloride (TFTPC), with various aromatic diamines were synthesized and characterized. The polyamides were obtained in high yields and moderately high inherent viscosities ranging from 1.07 to 1.16 dL/g. All the polyamides were amorphous and readily soluble in many organic solvents, such as N-methyl-2-pyrrolidinone (NMP), N,N′-dimethylacetamide (DMAc), N,N′-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), and could afford flexible and tough films via solution casting. The cast films exhibited good mechanical properties with tensile strengths of 82.8-107.3 MPa, elongation at break of 4.1-7.2%, and tensile modulus of 2.26-3.95 GPa. These polyamide films also exhibited good thermal stability with the glass transition temperature of 222-294 °C, the temperature at 5% weight loss of 442-472 °C in nitrogen. They exhibited low dielectric constants ranging from 3.25 to 3.39 (1 MHz), low moisture absorption in the range of 1.32-2.45%, high transparency with an ultraviolet-visible absorption cut-off wavelength in the 330-371 nm range, and excellent electrical properties.     

Signal amplification strategy for sensitive immunoassay of prostate specific antigen (PSA) based on ferrocene incorporated polystyrene spheres

A new kind of signal amplification strategy based on ferrocene (Fc) incorporated polystyrene spheres (PS-Fc) was proposed. The synthesized PS-Fc displayed narrow size distribution and good stability. PS-Fc was applied as label to develop immunosensors for prostate specific antigen (PSA) after the typical sandwich immunoreaction by linking anti-PSA antibody (Ab₂) onto PS-Fc. After the fabrication of the immunosensor, tetrahydrofuran (THF) was dropped to dissolve PS and release the contained Fc for the following stripping voltammetric detection. PS-Fc as a new electrochemical label prevented the leakage of Fc and greatly amplified the immunosensor signal. In addition, the good biocompatibility of PS could maintain the bioactivity of the antibodies. The response current was linear to the logarithm of PSA concentration in the range from 0.01 ng mL⁻¹ to 20 ng mL⁻¹ with a detection limit of 1 pg mL⁻¹. The immunosensor results were validated through the detection of PSA in serum samples with satisfactory results.     

Photopolymerization of waterborne polyurethane acrylate dispersions based on hyperbranched aliphatic polyester and properties of the cured films

A series of novel waterborne hyperbranched polyurethane acrylates for aqueous dispersions (WHPUD) based on hydroxy-functionalized hyperbranched aliphatic polyester Boltorn H20 were investigated and used as UV curable oligomers. The aqueous dispersions were electrostatically stabilized with carboxyl groups incorporated into their structures, which were neutralized by triethylamine. The photopolymerization kinetics of these WHPUDs was studied with respect to polymerization rates and unsaturation conversions in the presence of a photoinitiator using differential scanning calorimetry. The polymerization rates of the resins under UV irradiation and the gel contents in the cured films showed an increasing trend with higher concentration of acrylate functionality, which is in favor of the theory of radical chain polymerization. The mechanical and thermal behaviors of UV cured films of aqueous dispersions were evaluated by tensile testing and dynamic mechanical thermal analysis (DMTA). The results of DMTA investigations indicated that the glass transition temperature shifted to higher temperature as the content of the hard segment consisting of IPDI-HEA increased. Moreover, the storage modulus and pendulum hardness also increased with increasing the hard segment content. As the degree of neutralization increased, the T_g and tensile strength decreased, whereas, the elongation at break increased.     

Novel regular network polyester films from aromatic tetracarboxylic acids and ethylene glycol

Novel regular network polyester films were prepared from pyromellitic (X), biphenyltetracarboxylic (U), and 3,3′,4,4′-benzophenonetetracarboxylic (W) dianhydrides and ethylene glycol (2G). Prepolymers prepared by melt polycondensation were cast from DMF solution and successively post-polymerized at 260°C for various times to form a network. The resultant films were transparent, flexible, and insoluble in any solvents. The structure and properties of these network polyester films were compared with those of previously reported network polyester film from trimesic acid (Y) and 2G. Two diffraction peaks appeared in X-ray diffraction curves of 2GY, 2GX, and 2GU films. Peaks of 2GX and 2GU were broader than that of 2GY, suggesting less ordered structure of 2GX and 2GU by the less symmetric aromatic tetracarboxylic acid moieties. Densities of network films decreased with increasing the post-polymerization time. The degree of reaction (the degree of network formation) was estimated by the change of infrared absorption of hydroxyl and methylene groups. The degree of reaction obtained was 95 and 87% for 2GY and 2GX films post-polymerized for 12 h, respectively. Distortion temperature (T_h) was measured by a penetration mode of thermomechanical analysis (TMA). T_h, was 222 and 240°C for 2GY and 2GW films post-polymerized at 260°C for 12 h, respectively, while it disappeared for 2GX and 2GU films post-polymerized for more than 30 min and 1 h, respectively. Drastic decrease in TMA curves around 400°C corresponded to the rapid weight loss in TG curves due to the thermal decomposition. Young's modulus of network film was 2GX > 2GW = 2GU > 2GY, while the tensile strength and elongation were 2GY > 2GU > 2GW > 2GX. Water absorbing capacity was 2GX > 2GY > undrawn PET, while the alkali resistance was undrawn PET = 2GY > 2GX.     

Nickel(0)-catalyzed diastereoselective three-component coupling of 1,3-dienes, aldehydes, and organometallic reagents: influence of organometallic reagents on diastereoselectivity

A nickel-catalyzed diastereoselective alkylative three-component coupling of 1,3-diene and aldehyde with organoboron or organosilicon reagents has been realized. The diastereoselectivity was dramatically changed depending on the class of organometallic reagents. The reaction using ArB(OH)₂ in the presence of PPh₃ afforded 1,3-syn-substituted 4-penten-1-ol derivative as a single diastereomer. On the other hand, the coupling reaction with tetraorganosilicon reagent using NHC as a ligand under similar conditions exclusively produced the corresponding 1,3-anti isomer.     

Thermal stability and flame retardancy of PET/magnesium salt composites

Nano-Mg(OH)₂ (nanometre magnesium hydroxide, nano-MH) was successfully introduced into the esterification and polycondensation system by in situ polymerization to obtain PET/magnesium salt composites (PETMS). The thermal properties and flame retardancy of PETMS were investigated by differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), UL-94 vertical burning and limited oxygen index (LOI) test. The DSC and TGA results show that magnesium salts in the PET matrix have little effect on the thermal properties of PET, but a significant effect on the thermal stabilities of the composites. The results of LOI and UL-94 test show PETMS have higher LOI values (≥25%) and V-0 rating without melt dripping in the UL-94 test, indicating that PETMS have good flame retardancy and anti-dripping property. Moreover, the residues of magnesium salts and composites after TGA test were also studied by Fourier transform infrared spectroscopy (FTIR) to better understand the mechanism of flame retardancy, which reveals that magnesium salts accelerate the degradation of PET and catalyze the formation of char. The SEM results show the morphological structures of the char effectively protect the composites’ internal structures and inhibit the heat, smoke transmission and reduce the fuel gases when the fire contacts them.