新型Salen双肟化合物及其钴配合物的合成与表征

以3,5-二溴-2-羟基苯甲醛及1,4-二胺氧丁烷、1,3-二胺氧丙烷、1,2-二胺氧乙烷为原料,在无水乙醇溶剂中合成了3种新型的Salen双肟化合物。以Salen双肟化合物及乙酸钴为原料,合成了一种过渡金属Co配合物。采用IR、元素分析、1H NMR及TG-DTA等手段对化合物作了表征。结果表明,所合成的新型Salen双肟化合物与钴(Ⅱ)离子有较强的配位能力。     

一种新型Salen衍生物铜(Ⅱ)配合物的合成与表征

以无水乙醇为溶剂,1,2-二胺氧乙烷双缩3,5-二叔丁基水杨醛(H2L)与一水合乙酸铜反应,合成了一种新型Salen衍生物铜(Ⅱ)配合物。化合物经元素分析,1H NMR,IR,TG-DTA及UV等表征,结果表明,H2L是一种新型Salen型双肟类四齿配体,配合物的可能结构式为Cu(C32H46N2O4)。     

Salen型双肟配体及其铜(Ⅱ)配合物的合成与表征

以1,2-二胺氧乙烷和2'-羟基苯乙酮为原料,合成了Salen型双肟配体2,2'-[1,1'-(乙二氧二氮)二乙基]二酚(H2L).在甲醇-丙酮或乙醇-丙酮的混合溶剂中,H2L与乙酸铜反应,生成了两种不同结构的配合物,通过元素分析、1HNMR、FT-IR和UV-Vis等表征方法确定了配合物的可能结构为[CuL]·CH3...     

阿维菌素衍生物的化学合成

[目的]合成2种具有潜在抗虫活性的阿维菌素肟类衍生物。[方法]以阿维菌素B1为原料,将C-5位羟基氧化为酮基,再转化为肟基,得到单肟衍生物;以阿维菌素B1为原料,将C-13位的糖基水解为羟基,使用氯铬酸吡啶氧化C-5和C-13位的羟基为酮基,再转化为肟基,得到双肟衍生物。[结果]合成了阿维菌素C-5位单肟衍生物和阿维菌素C-5及C-13位双肟衍生物,经核磁共振确证了化学结构。[结论]为获得新的高效、低毒的绿色抗虫药提供了条件。     

Salen型化合物的合成和表征

用3-乙氧基水杨醛分别与两种新型二胺反应,共制备出两个对称的Salen型双肟化合物。它们分别为:6,6’-二乙氧基-2,2’-[1,2-亚乙二氧基双(氮次甲基)]二酚(H2L1)和6,6’-二乙氧基-2,2’-[1,3-亚丙二氧基双(氮次甲基)]二酚(H2L2),通过溶解性实验、元素分析和红外光谱分析测试方法对所得化合物进行了表征。     

嘧啶肟草醚的合成方法改进

以双草醚前驱体2,6-双[(4,6-二甲氧嘧啶基-2-基)氧]苯甲酸(简称双嘧啶水杨酸)、二苯甲酮肟为原料,采用酰化、DMAP催化缩合方式合成嘧啶肟草醚。本文研究开发的嘧啶肟草醚合成工艺,操作简便、反应条件温和、对生产设备无特殊要求、易于实现工业化、生产成本低,可提高产品收率及纯度。     

新型salamo衍生物苦味酸铜(Ⅱ)配合物的合成与表征

以丙酮为溶剂,1,3-二胺氧丙烷双缩邻香草醛(H2L)与苦味酸铜反应,制备了一种新型salamo衍生物苦味酸铜(Ⅱ)配合物,其结构经元素分析,1HNMR,IR,TG-DTA及UV表征。结果表明,新型salamo衍生物是一种四齿配体,配合物的可能结构式为[Cu4L2(pic)4(H2O)2].2CH3COCH3.2H2O。     

肟氨酯丙烯酸酯光-热双固化材料研究

为克服着色光固化体系固化不完全缺陷,解决预光固化、冲切变形后的涂层加硬问题,基于酮肟、二异氰酸酯、羟基丙烯酸酯,设计合成了 4种肟氨酯单丙烯酸酯及 2种肟氨酯双丙烯酸酯光固化材料。以红外光谱、实时红外光谱、漆膜性能测试及动态力学分析,研究了上述肟氨酯丙烯酸酯材料光固化涂层的基本性能,并考察了后热固化条件对光固化膜性能的影响。结果表明：光固化涂层的后热固化效能与树脂结构之间存在一定关联,脂肪族异氰酸酯 IPDI相较 TDI得到的肟氨酯丙烯酸酯解封更明显,甲乙酮肟相较苯乙酮肟得到的肟氨酯丙烯酸酯后热固化效果更显著。本研究为光-热双固化工艺提供了一种新的潜在选择。     

新型金属离子捕集剂—聚氧肟酸反相微乳液的合成及应用

采用微乳液聚合的方法合成了一种聚酰胺类的新型氧肟酸金属离子捕集剂。本文以液体石蜡作为分散相,Span-80作为乳化剂,与丙烯酰胺的环烷烃溶液复配成微乳液,加入盐酸羟胺并调节pH值进行羟肟化反应后,在低温下加入引发剂合成得到酰胺类氧肟酸的聚合物。研究了各种条件对产物性能的影响,采用红外光谱和粒度分析对产物结构进行表征,并考察其在金属离子废水处理中的脱除效果。结果表明,聚酰胺类氧肟酸金属离子捕集剂可以有效地捕捉到工业废水中的金属离子,且性能明显优于国内外同类产品。     

新型噻吩基二甲酸及其羟肟酸的合成与表征

以噻吩、水杨醛、SOCl2 和 NH2 OH· HCl为原料合成了 2种新型噻吩衍生物—— 2 ,5-双 [(2′-甲酸 )苯氧甲基 ]噻吩和 2 ,5-双 [(2′-甲酰羟肟酸 )苯氧甲基 ]噻吩 ,并对它们进行了元素分析、红外光谱、核磁和质谱表征。     

Novel porphyrazines containing peripherally functionalized macrocyclic (N2O2, N2S2) units: Synthesis and characterization

Novel maleonitrile moieties were synthesized by cyclization of 2,3-bis[(2-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile with 1,2-bis(2-iodoethoxy)-4-nitrobenzene or o-xylyenebis(1-chloro-3-thiapropane) under conditions of high dilution. A series of novel, free-base, magnesium and zinc porphyrazines bearing macrocyclic substituents in peripheral positions were prepared via Linstead macrocyclization reactions of different maleonitrile derivatives, 12-nitro-4,7-bis(pyridin-2-ylmethyl)-2,3,4,7,8,9-hexahydro-1,10,4,7-benzodioxa-diaza-cyclododecine-5,6-dicarbonitrile or 5,8-bis(pyridin-2-ylmethyl)-1,3,4,5,8,9,10,12-octa-hydro-2,11,5,8-benzodi-thiadiazacyclo-tetradecine-6,7-dicarbonitrile and the corresponding divalent metal salts. Pentanuclear copper(II) complexes were also prepared from the corresponding zinc(II) porphyrazine derivatives. The compounds were characterized by a combination of elemental analysis, FT-IR, UV–vis, ¹H NMR, ¹³C NMR and MS spectral data.     

Synthesis of a series of metallophthalocyanine end-capped poly(aryl ether sulfone)s from a dicyanoarylene group containing biphenol

A novel biphenol monomer, 1,4-bis(4-hydroxy-phenyl)-2,3-dicyanonaphthlene was prepared in high yield in a two-step reaction from reduced phenolphthalein containing a hydro cyanic group by an improved method. A series of uncapped copolymers were synthesized using this bisphenol. In addition, a series of thermally stable poly(arylene ether)s having covalently bound metal (II) naphthalocyanine units were synthesized by the reaction of dicyanoarylene containing poly(aryl ether)s with excess amounts of 1,2-dicyanobenzene and the corresponding metal salt in quinoline. The copolymers synthesized had high glass transition temperature and exhibited good thermal stability. Also, these polymers were found to have good solubility and capable of forming tough films. These colored polymers showed visible absorption maxima in the range of 538-715 nm.     

新型锰配合物的合成、多维结构及光催化性质研究

近年来,金属配合物的研究已经引起了广大研究者的兴趣,不仅是因为它们在催化、磁性、医学和材料科学等方面具有迷人的性质,而且还因为它们较强的协调能力以及各种协调模式,可以有助于构建有趣的框架。过渡金属配合物通过结合新颖的空间结构和过渡金属的特性,使其在降解处理环境污染物催化方面具有广泛的应用潜力。本课题通过水热合成法合成了一种新型的锰配合物[Mn(L)·H_2O](其中L表示1,4-二(2-甲基咪唑基)对苯甲酸),并通过红外光谱、元素分析和X射线单晶衍射仪进行了表征。从这个配合物的结构可以看到其具有孔洞结构,对其光催化性质具有一定影响。实验研究证明,该配合物在光催化降解处理有机染料方面具有良好活性。     

Organosoluble and light-colored fluorinated semialicyclic polyimide derived from 1,2,3,4-cyclobutanetetracarboxylic dianhydride

In this study, the alicyclic dianhydrides 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) was polymerized with seven kinds of fluorinated aromatic diamines, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (1), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (2), 1,4-bis(4-amino-2-trifluoromethylphenoxy)diphenyl (3), 1,4-bis(4-amino-2-trifluoromethylphenoxy) diphenyl ether (4), 2,2-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane (5), 4,4′-bis(4-amino-2-trifluoromethylphenoxy)diphenyl sulfone (6), and 2,7-bis(4-amino-2-trifluoromethylphenoxy)naphthalene (7), via a two-step polycondensation procedure to prepare seven kinds of fluorinated semialicyclic polyimides (PI) PI-1 ∼ PI-7. The structures of these polyimides were confirmed by infrared spectroscopy (IR). Solubility of the polyimides was tested in various organic solvents and their thermal properties were investigated by dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). Ultraviolet-visible spectra (UV-vis) and near infrared absorption spectra (NIR) were obtained to evaluate the optical properties of these polyimides. The obtained polyimides PI-1 ∼ PI-7 displayed excellent solubility in a variety of organic solvents; they were readily soluble in amide-type polar solvent. These polyimide films exhibited good optical transparency in the visible light region (400–700 nm) with the transmittance higher than 80% at 450 nm, and these polyimide films showed little absorption at the optocommunication wavelengths of 1.30 and 1.55 μm. These polyimides showed good thermal stability with the 10% thermal decomposing temperatures higher than 443°C in nitrogen and the glass transition temperatures higher than 265°C. In addition, the effect of the structure of fluorinated diamines on the properties of polyimide films was also compared. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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 and properties of novel poly(tetramethylsilnaphthylenesiloxane) derivatives

Novel poly(tetramethylsilnaphthylenesiloxane) derivatives were synthesized and characterized by differential scanning calorimetry (DSC), thermogravimetry (TG), and X-ray diffraction analyses. Poly(tetramethylsilnaphthylenesiloxane) derivatives were obtained by condensation polymerization of the corresponding disilanol derivatives, i.e. 1,4-, 1,5-, 2,6-, and 2,7-bis(dimethylhydroxysilyl)naphthalenes, which were prepared by the Grignard reaction using chlorodimethylsilane and the corresponding dibromonaphthalene derivatives followed by the hydrolyses, catalyzed by palladium on charcoal. The obtained poly(tetramethyl-1,5-silnaphthylenesiloxane) was insoluble in common organic solvents; however, the other polymers exhibited the good solubility in common organic solvents, such as tetrahydrofuran (THF), chloroform, dichloromethane, and toluene. The introduction of tetramethyl-1,5-silnaphthylenesiloxane units into the resulting polymer was confirmed by ¹H NMR spectrum of the copolymer obtained by condensation copolymerization of 1,5-bis(dimethylhydroxysilyl)naphthalene with 1,4-bis(dimethylhydroxysilyl)naphthalene. It was revealed from the DSC and X-ray diffraction measurements that poly(tetramethyl-1,5-silnaphthylenesiloxane) and poly(tetramethyl-2,6-silnaphthylenesiloxane) exhibited the crystallinity; however, poly(tetramethyl-1,4-silnaphthylenesiloxane) and poly(tetramethyl-2,7-silnaphthylenesiloxane) were amorphous. The glass transition temperature (T_g) and the temperature at 5% weight loss (T_d5) of poly(tetramethylsilnaphthylenesiloxane) derivatives with dimethylsilyl group at 1-position of the naphthylene moiety were higher than those at 2-position of the naphthylene moiety. The T_g and melting point (T_m) of the present polymers were higher than those of poly(tetramethyl-1,4-silphenylenesiloxane).     

新型噻吩基二醛及其缩氨基硫脲的合成

所合成的２，５－二（２－甲酰苯氧甲基）噻吩２及其缩氨基硫脲化合物２，５－二［（２’－甲酰缩氨硫脲基）苯氧甲基］噻吩３尚未见文献报道。对二者进行了元素分析、红外光谱、氢核磁共振谱、质谱及紫外－可见光谱表征。