Synthesis and properties of novel low band-gap polymers bearing squaraine units

<正>Novel main-chain-conjugated poly(carbazol-alt-squaraine) and poly(dipyridyl-alt-squaraine) were successfully synthesized through direct polycondensation of 9-(2-ethylhexyl)carbazole-bridged or dipyridyl-bridged bispyrrole and squaric acid.The structures and properties of the polymers were characterized using ~1H NMR,FT-IR,UV-vis and cyclic voltammetry.Both polymers exhibit excellent solubility in common organic solvents and good thermal stability.Their UV-vis absorption spectra indicated the polymers have broad and strong spectral responses from 200 nm to 900 nm,which reveals a low optical band gap around 1.38 eV, suggesting that they may be promising candidates for organic solar cells.     

Synthesis and characterization of novel low band-gap polymers containing squaraine units

Novel conjugated polymers based on squaric acid having 2,5-Bis[(E)-N-alkylpyrrol-2-ylvinyl]-3-alkylthiophene(PVTVP) unit in the main chain were successfully synthesized in good yields through polycondensation reaction.Their molecular structures were characterized by FT-IR and ~1H NMR.They have good solubility in common organic solvents,good thermal stability by thermal gravimetric analysis and high molecular weights.Their optical properties were investigated by UV-vis absorption spectra in CH_2Cl_2 solution,the results indicated all these compounds showed broad and strong spectral responses from 200nm to 900nm, suggesting their potential for application as organic plastic solar cells.     

Synthesis and characterization of novel conjugated polymers based on 3-cyclobutene-1,2-dione moiety

Three novel conjugated polymers bearing 3,4-bis（4-hexylthiophen-2-yl）-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,¹H NMR and ¹³C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers have good thermostability and solubility in common organic solvents.Moreover,all these objective macromolecules possess high electron affinity of～3.8 eV determined from cyclic voltammetry measurement,implying that they are potential n-type polymeric photovoltaic materials.     

新型双8-羟基喹啉配体及其锌、铝配位聚合物的合成和性能

合成2种双8-羟基喹啉配体:3,5-二[4-(8-羟基喹啉-5-亚甲氨基)苯氧基]苯甲酸辛酯(B8HQO)和3,5-二[4-(8-羟基喹啉-5-亚甲氨基)苯氧基]苯甲酸十六酯(B8HQH),进一步与Zn(Ⅱ)、Al(Ⅲ)配位,得到4种金属配位聚合物(B8HQO-Zn、B8HQH-Zn、B8HQO-Al和B8HQH-Al)。 通过元素分析、红外光谱(FIIR)、紫外可见光谱(UV-Vis)、核磁共振氢谱(¹H NMR)、电感耦合等离子体发射光谱(ICP-OES)、热重分析(TGA)及荧光光谱等测试手段对配体及金属配位聚合物进行结构表征和性能研究。 结果表明,与配体B8HQO和B8HQH相比,4种配位聚合物的溶解性降低,但可部分溶于N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAC)、二甲基亚砜(DMSO)和N-甲基吡咯烷酮(NMP)中。 锌、铝配位聚合物的5%失重温度分别在378和364 ℃附近,具有较好的热稳定性。 4种配位聚合物的DMF溶液(3×10^-5 mol/L)在478~502 nm发射绿色荧光,荧光量子效率28%~37%,固体在528~553 nm发射强绿色荧光,具有良好的发光性能。     

Synthesis of copolymers alternating oligophenylenevinylene subunits and fullerene moieties

Linear polymers alternating oligophenylenevinylene (OPV) moieties and C₆₀ subunits have been prepared in good yields by polycondensation of a bifunctional fullerene derivative with an OPV monomer bearing two alcohol functions. These polymers have been characterized by NMR, UV/vis and their molecular weights determined by size-exclusion chromatography coupled with light scattering.     

Novel fluorene-carzazole-based conjugated copolymers containing pyrazoline and benzothiazole segments for blue light-emitting materials

A series of novel fluorene-carbazole-based copolymers with pyrazoline and benzothiazole units were synthesized successfully through Suzuki coupling reactions.The molecular structures and thermal properties of these polymers were characterized by FT-IR, ~1H NMR,DSC and TGA.GPC results indicated that the weight-average molecular weight(M_w) and polydispersity of these polymers were in range(12,000-14,000)and(1.8-2.0),respectively.The two resulting polymers have high photoluminescence quantum efficiency implying that they may be promising candidates for polymer light-emitting diodes (PLEDs).     

Synthesis of Methyl—substituted Phthalazinone—based Aromatic Poly（amide imide）s

A series of novel aromatic poly (amide imide)s containing phthalazinone moietics were prepared from 2-(4-aminophenyl)-4-[3-methyl-4-(4-aminophenoxy)-2,3-phthalazinone-1], a novel diamine 1 with our diimide-dicarboxylic acids by Yamazaki phosphorylation method with the inherent viscosity of 0.36-0.65 dL/g. These polymers had high glass transition temperatures above 300℃ and they lost 10% weight between 426-475℃ in N2. The structure of diamine 1 and the polymers was confirmed by IR,^1H NMR and MS. The obtained polymers were readily soluble in polar solvents such as NMP,m-cresol etc. and easily cast into tough,flexible films. The X-ray indicated that they are all amorphous.     

以亲核取代反应制备质子交换膜用磺化聚酰亚胺

本文先通过缩合反应合成羟端基的二酰亚胺单体, 然后利用亲核缩聚反应, 与4,4′-二氯二苯砜及3,3′-二磺酸钠基-4,4′-二氯二苯砜共聚, 制备聚合物. 该合成路线反应周期短, 对温度和溶剂等条件要求不高, 简便易得.     

SYNTHESIS AND PROPERTIES OF POLY(AROMATIC DIACETYLENE)S CONTAINING FLUORENE

Novel fluorene-based poly(aromatic diacetylene)s have been synthesized by CuCl-catalyzed oxidative coupling of aromatic diynes.New aromatic diynes 2,7-diethynyl-9,9-bis(triphenylamine)fluorene(M_1)is synthesized by multistep reactions.The structures and properties of the polymers are characterized and evaluated by IR,NMR,TGA,UV, photoluminescence(PL),and cyclic voltammetry analyses.These polymers possess good thermal stability.All the polymers are completely soluble in coammon solvents such as toluene,TH...     

苯乙烯/丁二烯嵌段共聚物的氟烷基化改性

氧化物;苯乙烯/丁二烯嵌段共聚物的氟烷基化改性     

2-氧代-2-[1-(3-吡啶甲基氨基)-1′-芳基]甲基-4-芳基-5,5-二甲基-1,3,2-二氧磷杂环己烷的合成与生物活性

采用环状亚磷酸酯与亚胺的加成反应,合成了9个未见文献报道的含吡啶基的α-氨基环状膦酸酯化合物.其结构经1H NMR,31P NMR,MS和元素分析确证,同时采用X射线单晶衍射对化合物3i的立体构型进行了进一步确证.测定了该系列化合物的杀虫、杀菌和除草活性,结果表明,化合物的杀虫活性虽然较差,但所有化合物在药液质量浓度为1.0×10-4g/mL时都具有较好的除草活性,部分化合物在5.0×10-5g/mL时显示出良好的杀菌活性.     

聚苯基磷酸酯(PPP)的合成及其阻燃机制

阻燃剂;环氧树脂;聚苯基磷酸酯(PPP)的合成及其阻燃机制     

A SOLID NMR STUDY OF POLYETHERESTER-UREAS

The morphology of some polyetherester-ureas were studied by ~(13)C CP/MAS and ~1H wide-line NMR spectroscopy. It was found that the HDI and MDI based polymers have well crystallized hard segments, whereas the TDI and HMDI based ones have not. For HDI/MDI based polymers, the presented results suggest that the distribution of two kinds of hard segment units is mainly in a block form. The influences of the different hard segment and chain length on the mobility of the soft segment were also studied.     

Synthesis and characterization of new biodegradable thermosensitive polyphosphazenes with lactic acid ester and methoxyethoxyethoxy side groups

<正>Two novel biodegradable thermosensitive polyphosphazenes with lactic acid ester and methoxyethoxyethoxy side groups were synthesized via the macromolecular substitution reactions of poly(dichlorophosphazene) with the sodium salt of lactic acid ester and sodium methoxyethoxyethoxide.Their structures were confirmed by ~(31)p NMR,~1H NMR,~(13)C NMR,IR,DSC,and elemental analysis.The lower critical solution temperature(LCST) behavior in water and in vitro degradation property of the polymers was investigated.The results indicated that two polymers showed LCST phase transition over a range of concentrations from 0.13 to 15 wt%and pH-sensitive degradation properties.     

主链含N-烷基咔唑环结构聚芳醚酮的性能表征

对含N-烷基咔唑环结构的聚芳醚酮(PPCzE、PPCzB和PPCzH)进行基本物理性能方面的表征,并与商业化酚酞基聚芳醚酮(PEK-C)进行比较。 咔唑环结构的引入使聚合物在345 nm附近有强紫外光吸收并表现出发蓝光能力。 由于疏水性烷基侧链的存在,聚合物薄膜的水接触角(87°~103°)大于PEK-C(76°),但同时烷基侧链所引起的聚合物链间距的增大导致聚合物的吸水率(0.65%~0.86%)高于PEK-C(0.56%)。 此外,聚合物表现出较好的尺寸稳定性(平均线膨胀系数6.4×10^-5 ℃^-1)和电绝缘性能(体积电阻率10¹⁶ Ω·cm)。 聚合物的拉伸模量在1.9~2.0 GPa之间,拉伸强度在72.5~75.0 MPa之间以及断裂伸长率在6.5%~7.2%之间。 高温条件下(≤225 ℃),PPCzE仍具有良好的拉伸性能。     

Synthesis and neuroprotective properties of novel cinnamide derivatives

A new series of compounds （E）-1-（4-（bis-arylmethyl）piperazin-l-yl）-3-arylprop-2-en-1-one （1a-r）, have been synthesized and their structures were confirmed by ESI-MS and 1H NMR. The preliminary pharmacological screening showed that some of these compounds had similar neuroprotective effects with Edaravone.     

Novel photoluminescent polymers containing oligothiophene and m-phenylene-1,3,4-oxadiazole moieties: synthesis and spectroscopic and electrochemical studies

Three conjugated polymers containing oligothiophene units (from one to three thiophene rings) and aromatic 1,3,4-oxadiazole moieties have been successfully synthesized. The polymer structures were characterized and confirmed by (1)H and (13)C NMR, FT-IR, and elemental analysis. Thermogravimetric analysis demonstrated that the polymers are highly thermal stable. Tunable absorption (from 342 to 428 nm) and fluorescence (from 411 to 558 nm) properties of polymers were observed. The electrochemical investigation indicated that the LUMO and HOMO energy levels of the new polymers could be adjusted. It was also revealed by the electrochemical analysis that the polymers have good charge injection properties for both p-type and n-type charge carriers, as well as good color tunable luminescence and film-forming properties, which makes them potentially useful for fabricating efficient light-emitting devices.     

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.     

N-[5-(1-邻氯苯氧乙基)-1,3,4-噻二唑-2-基]-N′-芳酰基脲的合成及其生物活性

通过2-氨基-5-(1邻-氯苯氧乙基)-1,3,4噻-二唑与芳酰基异氰酸酯反应,合成了13种新的芳酰基脲。采用红外光谱,核磁共振氢谱和元素分析测试技术确证了结构。初步的生物活性测定试验表明,目标化合物具有良好的生长素活性,其中化合物2c、2d和2h的促进率分别为30.1%、32.5%和29.9%。     

一系列新的席夫碱型液晶高分子冠醚的合成与表征

以 4,4′ (α,ω 烷亚甲基二酰氧 )二苯甲醛和二氨基二苯并 1 5 冠 5为单体 ,采用溶液缩聚方法 ,合成了一类新的席夫碱型液晶高分子冠醚 .一种单体采用脂族二酰氯和对羟基苯甲醛反应制备 ,另一种新的单体采用二硝基二苯并 1 5 冠 5 ,在钯 碳催化剂存在下 ,水合肼还原制备 .合成的二硝基和二氨基 二苯并 1 5 冠 5 ,未能从IR和1 H NMR谱图上区分它们的几何异构体 .聚合物的分子量不高 ,Mn 在 1 0 1 0 0～ 1 3 0 0 0之间 .单体的结构通过元素分析、IR、1 H NMR和MS等方法确证 .聚合物的性质采用GPC、DSC、TG和POM等方法进行了研究 .发现所有的聚合物加热到各自的熔融温度 (Tm)以上都能形成液晶态 ,在液晶态可以观察到向列相的丝状织构和纹影织构 .聚合物的玻璃化转变温度 (Tg)、熔融温度和各向同性温度 (Ti)随聚合物分子中柔性间隔基的变化而变化 ,它们有较高的清亮点温度和宽的液晶态温度范围 .WAXD的研究进一步证实了聚合物的液晶性