3,4-二氢-1-(4-哌啶基)-2(1H)-喹啉酮的合成

以苄胺为原料,经6步反应得到新型抗高血压药OPC-21268的中间体3,4-二氢-1-(4-哌啶基)-2(1H)-喹啉酮,总收率13．9％．     

新试剂(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯的合成及其与汞的显色反应研究

合成了新试剂(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯(DCNPNPT),测定了试剂的亚氨基离解常数pKa＝9．2。在TritonX-100存在下,pH9．8～11．0范围内,试剂与Hg2+形成14黄色型配合物,用双波长法测得其表观摩尔吸光系数为2．27×105L·mol-1·cm-1。汞含量在0～10μg／25ml范围内符合比耳定律,用此法测定了天然水和实验室废水中微量汞含量,结果满意。     

以2,4-二苯基-4-甲基-1-戊烯为链转移剂的苯乙烯自由基聚合

以２,４ 二苯基 ４ 甲基 １ 戊烯（αＭＳＤ）为链转移剂,采用与环境友好的本体自由基聚合法及悬浮自由基聚合法合成了重均分子量Ｍｗ＝１,０００～５０,０００,分子量分布Ｍｗ／Ｍｎ≈２的苯乙烯低聚物．随着αＭＳＤ浓度的增加分子量降低效果明显,分子量分布明显变窄．热引发本体聚合物具有单端活性双键结构．     

4-（4′-丙基环己基）环己醇的合成

钌／碳催化剂应用于4-(4′-丙基环己基)苯酚(3PCO)的加氢反应，合成了4-(4′-丙基环己基)环己醇。以环己烷为溶剂，在98℃／2MPa，3PCO的转化率为100．0％，催化剂可以重复使用两次。     

4(2-吡啶偶氮)间苯二酚对钪(Ⅲ)与四-(4-三甲胺基苯基)卟啉显色反应催化机理的研究

在沸水加热的条件下,在pH 7．6的硼砂-盐酸缓冲介质中,单偶氮试剂PAR能加速Sc (Ⅲ)与四-(4-三甲胺基苯基)卟啉(TAPP)的反应,反应重现性好,配合物稳定,配合物组成为1:2, 配合物稳定常数为3．1×106,最大吸收波长位于421 nm,表观摩尔吸光系数为7．94×106L· mol-1·cm-1,Sc(Ⅲ)含量在0-0．04μg／10 mL范围内服从比耳定律。将拟定的方法应用于钛白粉中钪的测定,并测得回收率在92．0％-97．5％之间,初步探讨了催化反应的可能机理,认为:① Sc(Ⅲ)与PAR先形成活性的中间络合物,改变了溶液条件使与卟啉的反应易于进行;②带负电荷的PAR与带正电荷的卟啉之间形成缔合物使卟吩环变形,从而使与Sc(Ⅲ)的反应易于进行。     

2,4,4-三甲基-2-氯戊烷与1,1一二苯基乙烯的正碳离子反应(Ⅰ)──反应的主要特点

我们曾报道了合成异丁烯（PIB）类的遥爪聚合物及嵌段共聚物的新方法[1]．该方法的关键步骤——活性中心转化实际上是一可逆平衡反应．Faust等[2]以几乎同样的方法合成了异丁烯嵌段共聚物,但他们尚未意识到该反应是一可逆的平衡反应,相当于先增加一个单体单元,然后终止的聚合反应,在阳离子聚合反应中,这种典型、理想的反应极为少见,因此该反应有可能成为研究阳离子聚合的一个极好的模型反应．本文通过分析聚异丁烯端基的2,4,4-三甲基-2-氯戊烷（TMPCl）与DPE的反应产物,研究该反应的规律．1实验1．1试剂的纯化及合成CH2Cl2经…     

以Heck反应合成（E）-3-甲氧基-4，4′-二羟基二苯乙烯的研究

以香兰素为原料、以Heek反应为关键反应构建两苯环间乙烯桥，经四步反应、以Heek反应75．7％的收率和：50．3％的总收率合成了目标化合物(E)-3-甲氧基-4，4′-二羟基二苯乙烯(1)，并对Heek反应等反应条件进行了探讨．     

4-氨基-5-硝基-1,3-二氟苯重氮化反应机理研究

以4-氨基-1,3-二氟苯、乙酸酐和浓硝酸等为原料,合成了4-乙酰基-5-硝基-1,3-二氟苯,并且采用FT-IR和^1H NMR对产物进行了表征．采用量子化学方法,探讨了重氮化反应过程中重氮盐形成的微观机理,采用密度泛函理论（Density Functional Theory）在B3LYP／6．311G^＊＊水平下搜索得到反应路径,并对各中间体、过渡态和产物进行几何优化、振动频率分析和标准热力学函数计算;反应路径经过IRC验证．在MP2／6．311G^＊＊水平上对所有中间体、过渡态和产物进行更精确的能量校对．     

正庚基-氧-联苯基-4-氧一羰基]基-1-正戊炔的晶体结构研究

由于共轭聚合物的光致发光和电致发光性能，有望成为制造全塑性发光二极管的材料，因此近年来已引起人们的研究兴趣．聚乙炔是一种典型的共轭聚合物，其不稳定性和难加工性限制了它的应用．而含联苯液晶基元的取代聚乙炔，不仅其难加工性得到了改善，提高了稳定性，而且赋予了聚合物液晶性，因此有望开发出一批新型的高性能材料。     

微波法合成2，2＇-二苯-1，4-苯并噁嗪-3（4H）-酮及其结构表征

苯并噁嗪酮化合物广泛存在于禾本科植物中，这类化合物在前药合成和生物活性研究方面具有广泛的应用前景．目前已知的合成方法中，大多都是采用邻氨基酚与ClC（R1R2）COCl（氯酰氯）在碱性条件下长时间回流制得的，反应时间较长；除反应原料外，还需要加入其它碱性物质和溶剂．     

四氢呋喃/三氟化硼乙醚混合电解质中咔唑的电化学聚合

在四氢呋喃/三氟化硼乙醚混合电解质中直接阳极氧化咔唑制备聚咔唑.单体的起始氧化电位为0.92 Vversus SCE,远低于单体在含0.1 mol.L-1Bu4NBF4的乙腈溶液中的起始氧化电位(1.36 Vversus SCE).在此体系中获得的聚咔唑膜具有良好的电化学活性和稳定性,其电导率为7.0×10-3S.cm-1.聚合物可部分溶解于二甲基亚砜等强极性有机溶剂.UV-Vis,FT-IR,1H-NMR证明聚合物共轭长链的形成.该体系中获得的聚咔唑是一种蓝光发射材料,并具有良好的热稳定性.     

Organosoluble,low dielectric constant and highly transparent fluorinated pyridine-containing poly(ether imide)s derived from new diamine: 4-(4-trifluoromethyl)phenyl-2,6-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]pyridine

A new aromatic diamine, 4-(4-trifluoromethyl)phenyl-2,6-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]pyridine, was synthesized by a modified Chichibabin reaction of 4-(4-nitro-2-trifluoromethylphenoxy)acetophenone with 4-triflouromethylbenzaldehyde, followed by catalytic reduction. A series of fluorinated pyridine-containing aromatic poly(ether imide)s (PEIs) were prepared from the diamine monomer with various aromatic dianhydrides via conventional two-step thermal imidization method. The resulting PEIs had inherent viscosities values of 0.68–0.90 dL/g, and could be cast and thermally converted into transparent, flexible, and tough polymer films. These PEIs were predominantly amorphous, had good solubility in common solvents such as NMP, DMAc and m-cresol at room temperature, and displayed excellent thermal stability with the glass transition temperatures of 258–315?°C, the temperatures at 5% weight loss of 550–585?°C, and the residue of higher than 55% at 750?°C in nitrogen. Moreover, the PEIs films showed outstanding mechanical properties with tensile strengths of 74.8–103.5?MPa, tensile moduli of 1.08–1.45?GPa, and elongations at break of 10.6–24.4%. These PEIs also exhibited low dielectric constants of 2.81–2.98 (1?MHz) and water uptake 0.39–0.68%, as well as high optical transparency with the UV cutoff wavelength in the 350–378?nm range and the wavelength of 80% transparency in the range of 412–510?nm.     

一种含三氟甲基和呫吨结构聚酰胺的合成与性能

在浓硫酸和3-巯基丙酸催化下,3′-三氟甲基苯基-2,2,2-三氟苯乙酮(1)和甲苯于40～50℃下缩合反应8 h,制得中间体-1,1-二(4-甲基苯基)-1-(3′-三氟甲基苯基)-2,2,2-三氟甲基乙烷(2),继而在光照和N-溴代丁二酰亚胺促进下,将中间体氧化得到二羧酸-1,1-二(4-羧基苯基)-1-(3′-三氟甲基苯基)-2,2,2-三氟甲基乙烷(3),二步反应总收率为77.4%.采用Yamazaki体系,3和9,9-二[(4-氨基苯氧基)苯基]呫吨进行溶液亲核缩聚反应,制得了一种高分子量的(数均分子量为43000,分子量分布为1.8)新型含三氟甲基和呫吨结构的聚酰胺.该聚酰胺为非晶态结构并具有良好的透光率(λcutoff=330 nm),其玻璃化转变温度(Tg)为242℃,在氮气气氛中5%的热失重温度(Td5)为465℃,800℃时的残炭率为50%.聚合物易溶于N,N-二甲基乙酰胺(DMAc)、N-甲基吡咯烷酮(NMP)、间甲酚、吡啶(Py)和四氢呋喃(THF)等有机溶剂中,并可浇注得到韧性好和透明的薄膜,其拉伸强度为85 MPa,拉伸模量为2.0 GPa,断裂伸长率为10%.同时,该聚合物的体积电阻、表面电阻和介电常数分别为2.85×1015Ωcm,4.23×1014Ω和3.55(100 Hz),呈现了良好的电绝缘性能.     

Layer-by-layer deposition of rhenium-containing hyperbranched polymers and fabrication of photovoltaic cells

Multilayer thin films were prepared by the layer-by-layer (LBL) deposition method using a rhenium-containing hyperbranched polymer and poly[2-(3-thienyl)ethoxy-4-butylsulfonate] (PTEBS). The radii of gyration of the hyperbranched polymer in solutions with different salt concentrations were measured by laser light scattering. A significant decrease in molecular size was observed when sodium trifluoromethanesulfonate was used as the electrolyte. The conditions of preparing the multilayer thin films by LBL deposition were studied. The growth of the multilayer films was monitored by absorption spectroscopy and spectroscopic ellipsometry, and the surface morphologies of the resulting films were studied by atomic force microscopy. When the pH of a PTEBS solution was kept at 6 and in the presence of salt, polymer films with maximum thickness were obtained. The multilayer films were also fabricated into photovoltaic cells and their photocurrent responses were measured upon irradiation with simulated air mass (AM) 1.5 solar light. The open-circuit voltage, short-circuit current, fill factor, and power conversion efficiency of the devices were 1.2 V, 27.1 mu A cm(-2), 0.19, and 6.1x10(-3) %, respectively. The high open-circuit voltage was attributed to the difference in the HOMO level of the PTEBS donor and the LUMO level of the hyperbranched polymer acceptor. A plot of incident photon-to-electron conversion efficiency versus wavelength also suggests that the PTEBS/hyperbranched polymer junction is involved in the photosensitization process, in which a maximum was observed at approximately 420 nm. The relatively high capacitance, determined from the measured photocurrent rise and decay profiles, can be attributed to the presence of large counter anions in the polymer film.     

Electrosyntheses of freestanding poly (3-(4-fluorophenyl)thiophene) films in boron trifluoride diethyl etherate

High quality free-standing poly (3-(4-fluorophenyl)thiophene) (PFPT) films with conductivity of 10⁻¹ S/cm were electrosynthesized in boron trifluoride diethyl etherate (BFEE) by direct anodic oxidation of the monomer 3-(4-fluorophenyl)thiophene (FPT) on stainless steel sheet. As-formed flexible and shiny PFPT films can be cut into various shapes by a knife or a pair of scissors. The structure, thermal stability and morphology of PFPT films were studied by FT-infrared, UV-vis, Raman spectroscopy thermogravimetric analysis and scanning electron microscopy, respectively.     

Synthesis and characterization of poly[4-(4-hydroxyphenoxy) benzoic acid]

Poly[4-(4-hydroxyphenoxy) benzoic acid] was prepared by the bulk polycondensation of 4-(4-acetoxyphenoxy) benzoic acid. Polycondensation was conducted at 350°C for 3 h under a reduced pressure of 0.1 mmHg and gave a polymer with X?n of 255. The polymer was characterized by elemental analysis, IR spectroscopy, differential scanning calorimetry, and wide-angle X-ray measurement. The crystal/nematic and nematic/isotropic phase transition temperatures of polymer, which depend on the molecular weight, were observed at about 300°C and 410°C, respectively. The polymers with low molecular weights showed nematic textures above 300°C. This nematic/isotropic phase transition temperature is lower than that of poly (4-hydroxybenzoic acid). This thermal behavior of polymer comes from ether units, which increase the flexibility (the rotation or torsion of skeletal bonds) of the polymer chain. © 1994 John Wiley & Sons, Inc.     

含亚甲基和双二氮杂萘酮结构的聚芳酮的合成与性能

聚芳醚酮是一类重要的具有优异综合性能的工程塑料 ,它具有高的热稳定性、尺寸稳定性、耐溶剂性、好的加工性能和电性能 ,因而它经常作为复合材料的基质、粘合剂等被广泛的应用于航空、航天和电子等领域 .近几十年来 ,人们付出了很大的努力去开发聚芳醚酮新品种[1,2 ] .本研究组以 4 (4′ 羟基苯氧基 ) 2 ,3 二氮杂萘 1 (2Ｈ) 酮为缩聚单体制备了一系列的性能优良的聚芳醚酮[3～ 6] ,在主链中引入高密度的氮杂萘酮结构是获得高热稳定性和良好溶解性的重要途径 .由单体中含有更多的氮杂萘酮结构获得可溶解且耐温等级更高的聚芳酮是人们期…     

Synthesis of nonlinear optical polymers with large photoconductive sensitivity and transparency

Novel nonlinear optical (NLO) chromophore, 2-{3-[2-(4-methylsulfonylphenyl)vinyl]carbazol-9-yl}ethanol was synthesized and subsequently reacted with methacryloyl chloride to give a photoconducting NLO monomer ( M1 ). 2-Methylacrylic acid 2-[3-(diphenylhydrazonomethyl)carbazol-9-yl]ethyl ester ( M2 ) was also synthesized as a comonomer to enhance the carrier mobility of the NLO polymer. Photoconducting NLO polymers, P1 and P2 were obtained by the copolymerization of Ml with methyl methacrylate and M2 , respectively. These polymers were well soluble in organic solvents and showed glass transition at 177 °C and 196 °C, respectively. Polymer films of P1 and P2 were optically clear, and were transparent at wavelengths longer than 420 nm. The electro-optic coefficient (r₃₃) of poled P1 films was measured to be ∼5 pm/V at 632.8 nm. The photoconductive sensitivities of P1 and P2 were 6.2 × 10⁻¹⁴ S·cm⁻¹/mW·cm⁻² and 5.6 × 10⁻¹¹ S·cm⁻¹/mW·cm⁻².     

Immobilization of Tris-(8-hydroxyquinoline) aluminum onto P4VP polymer thin films by UV irradiation cross-linking

We report a novel method for the immobilization of Tris-(8-hydroxyquinoline) aluminum (Alq₃) onto poly(4-vinylpyridine) (P4VP) thin polymer films by UV irradiation cross-linking. The polymer films were prepared by spin-coating of P4VP onto cleaned silicon wafer surface followed by UV irradiation. The thicknesses of the polymer thin films were measured by ellipsometry with different irradiation times. The immobilization of Alq₃, orientation and the surface activity were followed using photoluminescence and UV-visible spectroscopy. The surface morphology was investigated by using field emission scanning electron microscopy and atomic force microscopy. Patterning of Alq₃ on P4VP film was obtained using photolithography technique. Our experimental results show that the cross-linked P4VP thin film is a universal surface modifier.     

Ultrafast photoinduced charge separation dynamics in polythiophene/SnO2 nanocomposites

We present a study of photoinduced interfacial electron transfer (ET) dynamics of SnO2 nanocrystalline thin films sensitized by polythiophene derivatives (regioregular poly(3-hexylthiophene) (P3HT) and regiorandom poly(3-undecyl-2,2'-bithiophene) (P3UBT)). ET dynamics were measured by following the dynamics of injected electrons in SnO2 and polarons in the conjugated polymer using ultrafast mid-IR transient absorption spectroscopy. The rate of electron transfer from P3HT and P3UBT to SnO2 films was determined to occur on sub-picosecond time scale (120 +/- 20 fs). In P3HT/SnO2 composite, interchain charge transfer was found to compete with and reduce the quantum efficiency of interfacial electron transfer at high polymer loading. This interchain charge separation processes can be reduced in non-regioregular polymer or at low polymer loading levels.