Synthesis and photocatalytic properties of iron(II)tetramethyl- tetra(1,4-dithiin)porphyrazine

The titled complex has been synthesized according to the template method from the prepared intermediate of 2,3-dicyano-5-methyl-1,4-dithiin in the presence of iron(II)sulfate heptahydrate and characterized by UV–vis, FT-IR , ¹H NMR, XPS and elemental analysis. The complex was supported on an Amberlite CG-400 resin to form a biomimetic catalyst, the ability of which for activating molecular oxygen was estimated from the degradation of Rhodamine B (RhB) under visible light irradiation in an aerated suspension. About 78% of the RhB was degraded in 27 h with a rate constant of 1.84 × 10⁻¹⁰ mol L⁻¹ s⁻¹. Aggregation between the dimer and monomer for the titled complex in DMSO or in DMF solution was observed from the concentration dependence in the UV–vis spectra. The effect of the aggregation was also demonstrated by the diffuse reflectance spectral measurement for the catalyst supported on the resin in saturated and supersaturated adsorption conditions. The monomer of catalyst has a higher capability to activate molecular oxygen for the degradation of organic pollutants than that of an aggregation form.     

四溴丙基四(1,4-二噻(口英))四氮杂卟啉锌的合成及其性能研究

以镁离子为模板,2,3-二氰基-5-溴丙基-1,4-二噻(口英)为前驱体,成功地合成了四溴丙基四(1,4-二噻(口英))四氮杂卟啉锌,用紫外光谱、红外光谱、元素分析和X-射线光电子能谱对其进行了表征,并将目标化合物负载到树脂上,初步考察了其对苯酚的光催化降解效果.     

四酰胺基四(1,4-二噻英)四氮杂卟啉的合成

以2,3-二氰基-5-酰胺基-1,4-二噻英为前驱体,利用镁模板法在较温和的条件下合成了四酰胺基四(1,4-二噻英)四氮杂卟啉自由配体,目标产物的终产率为42%,并通过1H-NMR、UV-Vis、XPS等表征手段进行了初步表征。有待进一步合成四酰胺基四(1,4-二噻英)四氮杂卟啉金属配合物。四酰胺基四(1,4-二噻英)四氮杂卟啉金属配合物可用于在模拟太阳光的条件下降解罗丹明B、甲基橙等染料。     

长链烷基二甲基聚甘油基氯化铵的合成与性能

以甘油、N,N-十二烷基二甲基叔胺(DTA)与环氧氯丙烷(ECH)为主要原料合成了一种表面活性剂长链烷基二甲基聚甘油基氯化铵。考察了反应时间、温度和反应物质的量比对合成产率的影响,并测得该表面活性剂的表面张力为γ=28.14 mN/m、临界胶束浓度cmc为0.112 g/L,初步的性能研究结果表明,该表面活性剂即使在高浓度的电解质溶液中亦具有很好的溶解性,且与阴离子表面活性剂具有优异的配伍性,能以任何比例与阴离子表面活性剂复配。     

三(戊烷氧基)苯-一(1,4-二噻英)四氮杂卟啉的合成

前驱体2,3-二氰基-1,4-二噻英由顺式-1,2-二氰基-1,2-乙二硫钠盐与1,2-二溴乙烷反应生成,前驱体4-戊烷氧基邻苯二腈由正戊醇与4-硝基邻苯二腈反应得到,然后用"镁模板法"合成不对称的三(戊烷氧基)苯-一(1,4-二噻英)四氮杂卟啉,产率为43%。并对其自由配体进行了紫外光谱和Maldi-TOF MS表征。     

长链烷基季铵碱的制备工艺及性能研究

以烷基叔胺和碳酸二甲酯为原料制备烷基碳酸甲酯铵,烷基碳酸甲酯铵水解得到烷基碳酸氢铵,再通过离子膜连续电解法合成长链烷基季铵碱。以十四烷基三甲基氢氧化铵为例,考察了电解反应温度、电流密度、阳极液浓度、阴极出料液浓度对电流效率的影响,得出其最优工艺条件为：反应温度65 ℃、电流密度450 A/m2、阳极液浓度1.40 mol/L、阴极液出料浓度为0.15 mol/L,在此条件下电解反应的电流效率可达67%以上;通过1H-NMR、IR对产品结构进行了鉴定,结果表明合成的产品为长链烷基季铵碱;对得到的长链烷基季铵碱的表面活性、pH值、润湿性、泡沫稳定性等性能进行了研究。     

一种新型仿生化合物四甲基四(1,4-二噻)四氮杂卟啉锰的合成与表征

成功合成了新型化合物2,3-二氰基-5-甲基-1,4-二噻,进一步以其为前驱体用模板反应法合成出四甲基四(1,4-二噻)四氮杂卟啉锰,用紫外-可见光谱、红外光谱、元素分析和X-射线光电子能谱对配合物进行了结构表征。     

一种新型仿生化合物四甲基四(1,4-二噻(口英)四氮杂卟啉锰的合成与表征

成功合成了新型化合物2,3-二氰基-5-甲基-1,4-二噻(口英),进一步以其为前驱体用模板反应法合成出四甲基四(1,4-二噻(口英))四氮杂卟啉锰,用紫外-可见光谱、红外光谱、元素分析和X-射线光电子能谱对配合物进行了结构表征.     

四苯乙炔基硅烷的合成及热性能研究

为得到耐热的含有苯乙炔官能团的有机硅单体,通过苯乙炔锂(由苯乙炔与丁基锂制得)与四氯硅烷的反应,合成了四苯乙炔基硅烷(TPES),通过多次重结晶获得了纯度为99.5%的TPES,并用FTIR、1HNMR、13C NMR、29Si NMR及元素分析对其结构进行了表征。对TPES及其400℃固化物的DSC、FTIR和TGA的分析表明:TPES的熔融温度范围宽达113℃(199℃~312℃);在氮气中失重5%时的温度Td5为710.8℃,800℃残炭率高达93.3%,空气中的Td5为595℃,800℃残炭率也达58.3%,耐热性能十分优异,具备作为一种耐高温聚合物材料的优秀潜质。     

新型仿生分子四酯基四(1,4-二噻英)四氮杂卟啉及其金属配合物的合成与表征

以2,3-二氰基-5-酯基-1,4-二噻英为前驱体、以Mg2+为模板成功地合成了新型仿生化合物四酯基四(1,4-二噻英)四氮杂卟啉镁[MgPz(H3COOC-dtn)4]及其自由配体[H2Pz(H3COOC-dtn)4],用紫外可见光谱、红外光谱、质谱、X-射线光电子能谱对其进行了结构表征。     

一种新型四羧基(1,4-二噻英)四氮杂卟啉镁季铵盐的合成与表征

成功合成了四羧基(1,4-二噻英)四氮杂卟啉镁[MgPz(dtn-COOH)4]及其十六烷基三甲基铵盐[MgPz(dtn-COO-.CTA+)4],并通过紫外可见光谱、红外光谱和荧光光谱对其进行了表征。结果表明,季铵盐的形成很好地改善了四羧基(1,4-二噻英)四氮杂卟啉镁的溶解性能;季铵盐不仅易溶于常见的有机溶剂,还可以很好地溶于不同pH值的水溶液。     

Synthesis and chiroptical properties of helical poly(phenylacetylene) bearing optically active chiral oxazoline Pendants

The novel optically active (S)-4-benzyl-2-(ethynylphenyl)-oxazoline (BnEPhOx) was successfully prepared and polymerized using rhodium catalyst ([Rh(nbd)Cl]₂) to obtain the moderate molecular weight poly(phenylacetylene)s bearing chiral oxazoline derivatives with high yields (≥90%). The ¹H NMR spectra demonstrated that the resulting polymers had high stereoregular structures. Moreover, the poly(phenylacetylene)s bearing chiral oxazoline exhibited better thermal stability than poly(phenylacetylene). The resulting polymers showed higher absolute values of optical specific rotation than the monomer. The polymers also exhibited intense CD signal in the region of the π-π1 band of the conjugated polyacetylene backbone in chloroform solution. The results of specific rotation and CD spectroscopy indicated that all the polymers adopted higher-order structure with predominantly one-handed screw sense.In addition, the resulting polymers emitted fluorescence under UV irradiation.     

Synthesis and luminescence properties of long-chain (2,7-carbazolyl)-adamantane copolymers

Several long-chain (2,7-carbazolyl) adamantane copolymers, with molecular weight ranging from 4500 to 6000, were synthesized by palladium-catalyzed Suzuki reaction using 1,5-bis (4-bromophenyl) adamantane and N-(2-ethylhexyl)-2,7-carbazole as building molecules. The copolymers were characterized by infrared, ultraviolet, nuclear magnetic resonance (NMR), fluorescence spectroscopies, and thermal analysis. It was found that the introduction of adamantyl group into the backbone of conjugated carbazole polymer significantly improves the thermal stability and spectral stability of the copolymer. These copolymers giving high color purity showed excellent comprehensive performance: the thermal decomposition temperature is up to 409 ~ 432 °C, glass-transition temperature is about 83 ~ 162 °C, fluorescence quantum efficiency is as high as 0.76 ~ 0.85. Hence, the synthesized copolymers have great potential for being used as new blue-light-emitting materials.     

Synthesis and properties of poly (1,4-cyclohexanedicarboxylic anhydride)

Summary Polyanhydrides from cycloaliphatic 1,4-Cyclohexanedicarboxylic acid (1,4-CHDA) were synthesized by melt polycondensation and characterized by WAXD, FTIR and DSC. The results show that these polymer displayed strong crystallinity with highly melting point and can't be dissolved in common solvents. The polymers, which come from different original isomer conformation CHDA, show different melting point and DSC curve. The isomerization happened during the polymerization and reached an equilibrium point at last. By melt polycondensation, the high cis-isomer content polyanhydride is difficult to obtained. Received: 24 May 2000/Revised version: 4 September 2000/Accepted: 6 September 2000     

Surface active hydroxamic acids. I. Preparation and properties of long-chain alkyl[oligo(oxyethylene)] oxymethylenehydroxamic acids

For the development of surfactants having an ability to interact with metal ions, hydroxamic acids containing a long-chain alkyl[oligo(oxyethylene)] group were prepared. Any hydroxamic acid with an octyl, decyl or dodecyl group was made readily soluble in water by introducing four oxyethylene units into the molecule. These water-soluble hydroxamic acids had a micelleforming ability and acted as polyoxyethylene-type nonionic surfactants under acidic and neutral conditions. Additionally, those compounds were found to form a water-soluble complex with ferric ion at pH 2, and these complexes also showed surface active properties.     

熔融法无溶剂一步催化合成四（1,4-二噻英）四氮杂卟啉锰

首次以2,3-二氰基-1,4-二噻英为原料,钼酸铵为催化剂,四水合氯化锰为模板,用熔融法无溶剂一步合成了标题化合物,其结构经过UV-Via、IR、元素分析、X-射线光电子能谱(XPS)表征.     

Highly active and selective ethylene oligomerization catalysts: Asymmetric 2,6-bis(imino)pyridyl iron (II) complexes with alkyl and halogen substitutients

A series of asymmetric 2,6-bis(arylimino)pyridines with alkyl and halogen substitutients on different iminoaryl rings and corresponding iron (II) complexes ([2-(Ar₁N = CCH₃)-6-(Ar₂N = CCH₃)C₅H₃N]FeCl₂, 3a–3j) are synthesized and characterized. These Fe(II) complexes are highly active for ethylene oligomerization with high selectivity for linear α-olefins. The oligomer distributions can be tuned by the synergism of alkyl-steric effect and halogen electronic effect, and the production of C₆–C₁₆ can reach more than 80% with the highest selectivity being 87.5% for 3 g (Ar₁ = 2-ethylphenyl, Ar₂ = 2-fluorophenyl), which is 15–30% higher than that catalyzed by their methyl or fluoro-substituted symmetric counterparts.     

Synthesis,characterization, and optical properties of polymers comprising 1,4-dithiane-2,5-bis(thiomethyl) group

To obtain an optical polymer with a high refractive index (n_D) and Abbe's number (ν_D), a series of 1,4-dithiane-2,5-bis(thiomethyl) (DBT) group-bearing poly(S-alkylcarbamate) and polyvinylsulfide were synthesized by the polyaddition of 2,5-bis(mercaptomethyl)-1,4-dithiane (BMMD) with diisocyanates and by the addition polymerization of 2,5-bis(2-thia-3-butenyl)-1,4-dithiane (TBD) in bulk, respectively. Their n_D : ν_D values, ranging from 1.598 : 38.2 to 1.678 : 34.8, are comparable to those of flint glass. Some of the polymers having a high transparency and glass transition temperature were suggested to be useful as optical polymers. The DBT group contribution to the increase of the n_D value of the obtained polymer was explained in terms of the value defined by the ratio of molar refraction to molar volume and was concluded to be of primary importance because the value for the DBT group (0.38) was greater than that for the residual group making up the polymer structure. This group's contribution in preventing the degradation of the ν_D of the polymers was also discussed based on the UV spectrum of BMMD, which only showed a suppressed absorption band. BMMD and TBD are useful monomers for preparing an optical polymer with high n_D and ν_D values. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1791–1799, 1998     

Synthesis and properties of poly(ethylene-1,4-cyclohexanedimethylene naphthalate)

Copolyesters were synthesized from bis(hydroxyethyl) naphthalate/bis(hydroxymethylcyclohexane)naphthalate (BHEN/BHCN) with various compositions. Copolyesters having intrinsic viscosities of 0.58–0.65 dL g were obtained by melt polycondensation in the presence of metallic catalysts. The optimum condition for polyethylene-1,4-cyclohexanedimethylene naphthalate (PECN) copolyester manufacturing is the transesterification under a nitrogen atmosphere for 4 h at a temperature of 245 ± 5°C followed by polymerization under 2 mmHg for 50 min at a temperature of 290–320°C. Most copolyesters have better thermal stability than has poly(ethylene naphthalate) (PEN) and the effect of the cyclohexane–dimethylene structure on the thermal and crystalline properties of the resulting copolyesters was investigated using differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Glass transition temperatures of the copolyesters were in the range of 115.2–138.4°C, and 10% weight losses in nitrogen were all above 453°C. The solubility, crystallinity, and moisture absorption of the copolyesters were also investigated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2245–2252, 1998     

Synthesis and characterizations of nanosized iron(II) hydroxide and iron(II) hydroxide/poly(vinyl alcohol) nanocomposite

Nanosized Fe(OH)₂ was synthesized by a coprecipitation method. Peaks between 500 and 1250 cm^?1 in Fourier transform infrared (FTIR) spectroscopy confirmed the presence of metal hydroxide stretching. X‐ray diffraction showed the suppressed crystalline system of Fe(OH)₂/aniline (ANI) due to the presence of a higher weight percentage of the dispersing agent, ANI. Thermogravimetric analysis implied that 75.5 wt % of residue remained up to 800°C. High resolution transmission electron microscope (HRTEM) analysis of Fe(OH)₂/ANI revealed that its size ranged from 10 to 50 nm with a rodlike morphology. Scanning electron microscopy implied that pristine Fe(OH)₂ had a nanotriangular platelet morphology, and a higher weight percentage of dispersing agent intercalated with Fe(OH)₂ had a spheroid with an agglomerated structure. The (UV–visible) spectrum implied the presence of Fe²⁺ ions at 326 nm and the existence of an amino group intercalated with Fe(OH)₂ showed a sharp peak at 195 nm, the intensity of which increased with increasing intercalated dispersing agent weight percentage. Photoluminescence showed that ANI‐intercalated Fe(OH)₂ showed a lesser intensity than the pristine Fe(OH)₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010