聚(芳基醚1,3,4-噁二唑)类聚合物的合成及表征

为改善芳香族聚噁二唑的加工性,合成了一种含噁二唑的双氟单体,将其与二酚单体进行溶液缩聚,得到一系列含有醚键与C(CH3)2,CCH3C6H5等官能团的新型聚(芳基醚1,3,4-噁二唑)(PEOD),其黏度达1.0 dL/g,噁二唑成环率达100%,并通过核磁氢谱(1H-NMR)和元素分析(EA)证实了其化学结构。通过热重分析(TGA)对PEOD的热稳定性进行了表征,结果表明,这些聚合物具有优良的热性能。通过溶解性试验表明PEOD能够溶解于三氯甲烷(CHCl3)、二氯甲烷(CH2Cl2)、四氢呋喃(THF)等有机溶剂,其溶解性比聚对苯撑噁二唑(p-POD)及对间苯噁二唑(p/m-POD)有了较大的改善。     

新型聚噁唑烷酮的合成与表征

采用甲苯二异氰酸酯与自制的对苯二甲酸二缩水甘油酯生成聚噁唑烷酮.并用红外光谱、DSC、热重分析仪对其进行表征.检测出其玻璃化温度为110℃,其失重5%时需要的温度为257℃,并研究了其绝缘性能.     

含苯并噁唑半芳香聚酰胺的合成与表征

为了得到同时具有优良耐热性能和易加工性能的新型半芳香聚酰胺,以5-氨基-2-(对氨基苯)苯并噁唑(ABO)和己二酸基于Yamazaki磷酸化过程合成了聚己二酰对苯撑苯并噁唑二胺(BO6).研究了反应温度对聚合物分子量的影响,并通过FTIR、1H-NMR对其结构进行了表征;利用DSC、TG对其热性能进行了研究.结果表明:反应温度在90℃左右时高聚物获得了最高的粘数.该聚合物的耐热性较脂肪族聚酰胺有较大幅度的提高,同时该聚合物具有较好的耐溶剂性能.     

含硝基噁二唑聚炔的合成及三阶非线性光学性能

设计合成了一种含硝基噁二唑功能基的聚炔材料。通过红外光谱(IR)和核磁共振(1H-NMR)对该聚炔化合物进行了结构表征。利用紫外光谱(UV-vis)和热重分析(TGA)对其性能进行了评价。TGA显示其热稳定性相对于单体有很大提高,UV-vis表明它在500 nm以上长波区吸收很弱。该聚炔化合物的非线性光学性能借助Z-scan技术进行研究,其χ(3)达3.25×10-11(esu)。与含烷基的同类聚炔比较,拉电子基团硝基有效地提高了含噁二唑聚炔的三阶非线性光学性能。     

噁二唑类电子传输材料的研究进展

1,3,4-噁二唑环是一个具有高电子亲和势和空穴阻挡作用的基团,含该基团的化合物是一类具有发光性能的电子传输材料.本文综述了对含1,3,4-噁二唑环的有机小分子、星状、枝化分子和聚合物的电子传输材料的进展,并且对该类化合物作了简要的展望.     

主链含柔性亚甲基苯并二噁唑类聚合物的合成及性能研究

设计并合成了一系列含有苯并噁唑环和不同CH2链长的刚、柔间隔聚亚甲基苯并二噁唑（PBOCx）聚合物，并对它们进行了结构表征，同时对聚合物的溶解性能和热性能进行了探讨．研究表明，在主链上引入亚甲基结构可以在一定程度上提高聚合物的溶解性，其中PBOC4显示了良好的溶解性能，但随着亚甲基数目的增加，聚合物的溶解性能有下降趋势；虽然有柔性链段的引入，分解温度降低，但是PBOCx仍具有很高的热分解温度，在450℃以下表现出良好的热稳定性．     

单(噁)二唑席夫碱的合成与光谱研究

4-硝基苯甲酸经酯化和肼解后制得4-硝基苯甲酰肼(2),再与苯甲酰氯反应得到N-苯甲酰基-N’-(对硝基苯甲酰基)-肼(3),(3)在SOCl2存在下脱水环化生成2-苯基-5-(对硝基苯基)-1,3,4-(噁)二唑(4),(4)被Zn/CaCl2还原为2-苯基-5-(对氨基苯基)-1,3,4-(噁)二唑(5),(5)与...     

苯并二噁唑系列聚合物的合成及其光电性能的研究

以4,6-二氨基-1,3-苯二酚盐酸盐为原料,分别与对苯二甲酸、1,4-萘二甲酸、2,6-萘二甲酸、2,5-噻吩二甲酸、4,4’-(1,2-二苯基乙烯)二甲酸、反丁烯二甲酸在多聚磷酸介质中反应,合成了单环的聚(1,4-亚苯基)苯并二噁唑(PBO)、稠环的聚(1,4-亚萘基)苯并二噁唑(1,4-PNBO)和聚(2,6-亚萘基)苯并二噁唑(2,6-PNBO)、杂环的聚(2,5-亚噻吩基)苯并二噁唑(PTBO)、含有两个苯环的聚-4,4’-亚(1,2-二苯乙烯基)苯并二噁唑(4,4’-PDPEBO)和直链烯烃的聚亚乙烯基苯并二噁唑(PBOV)。采用傅立叶红外光谱、元素分析对系列聚合物的结构进行了表征。利用电导率仪和荧光光谱仪,对系列聚合物的结构与性能之间的关系进行了分析。研究结果表明,PBO、1,4-PNBO、2,6-PNBO、4,4’-PDPEBO、PTBO和PBOV电导率依次减小;系列聚合物的荧光发射光谱和激发光谱的形状都相近,聚合物的最大发射峰波长是一致的,其中2,6-PNBO的荧光强度最强。     

含咔唑结构二胺的合成及其表征

通过亲核取代反应由3,3'-联咔唑和对氯硝基苯合成含咔唑结构的二硝基化合物,并对其还原,得到一种含咔唑结构的二胺,该二胺具有空穴传输基团.用红外光谱、飞行质谱、核磁氢谱及紫外光谱等对该化合物进行了表征.     

聚噁二唑芳亚胺联噻吩的合成及性能

以3,3’-二溴-2,2’-联噻吩和2,5-二(4-氨基苯基)-1,3,4-噁二唑为单体,通过钯催化CAr-N偶联合成了新型功能高分子聚噁二唑芳亚胺联噻吩(POXDIBT)。通过分子模拟、傅里叶变换红外光谱、核磁共振氢谱、热重、紫外可见吸收光谱、荧光光谱等分析技术对聚合物的分子结构、分子链构象、热稳定性及光学性能进行了研究。结果表明,该聚合物呈现锯齿形分子链构象,具有较好的溶解性能,热分解温度Td=323℃,在339nm处具有强吸收,激发波长为340nm时,荧光发射波长为401nm。     

含咔唑PPV类超支化聚合物的合成及性能

以CpCo（CO）2为催化剂在紫外光照射的条件下，以3，6-二[（4-乙炔基）苯乙烯基]-N-辛基-咔唑双炔和1-辛炔作为单体，通过[2＋2＋2]环三聚反应合成了含咔唑PPV类超支化聚合物。采用红外光谱、核磁共振谱、热失重分析、紫外吸收光谱、荧光光谱、循环伏安法等方法对聚合物进行结构表征与性能测试，所得到的聚合物都溶于普通的有机溶剂（比如四氢呋喃、二氯甲烷、氯仿、甲苯等）。这类聚合物都表现出优异的热稳定性，它们的起始分解温度在378℃以上，在800℃时，聚合物的残余碳化率高达63％；荧光光谱显示，在光激发的条件下，聚合物在二氯甲烷溶液中发射蓝光，其荧光量子效率高达80％，电化学分析表明聚合物具有较好的空穴传输能力。     

Synthesis and electroluminescence properties of novel silicon-based copolymers containing oxadiazole and fluorene units for PLED

Novel silicon-based copolymers containing an electron-deficient oxadiazole unit and a fluorine unit have been successfully synthesized through the Heck reaction. They are soluble in common organic solvents such as THF, CHCl₃, etc. Their UV–visible absorption spectra exhibit a strong maximum band at the range of 355–381 nm in thin film. Upon a photoexcitation of 350 nm, their photoluminescence spectra show a strong maximum band around 455–475 nm in thin film. The multi-layered light-emitting diodes (LEDs) of Al(200 nm)/Ca(50 nm)/EL polymer(80 nm)/PEDOT(50 nm)/ITO were fabricated. J–V curves show the turn-on voltage in the range of 4.4–7 V. These LEDs emit the white emissive color, due to the combination of a blue electroluminescent (EL) color and a red EL color arising from the formation of a certain charge complex.     

Synthesis and characterization of conjugated low band-gap terpolymers incorporating carbazole for photovoltaic application

A series of photoactive conjugated low band-gap copolymer (CPSB) and terpolyemrs (TPSBCz-n, n = 1 to 4) based on N-alkyl carbazole, 4,4'-dialkyl dithienosilole, and bezothiadiazole were synthesized. The copolymer and terpolymers were built with the fraction of the carbazole unit varied for 0, 2.5, 5, 10 and 25 mol%. Among the mixtures, the composition of 25 wt% of terpolymer bearing 10 mol.% of the carbazole unit, TPSBCz-3, and 75 wt% of C71-PCBM found a power conversion efficiency of 0.86% with a open-circuit voltage of 0.59 V, the short-circuit current of 4.85 mA and fill factor of 0.30 under AM 1.5 spectral illumination. Our findings suggest that terpolymer bearing low concentration of carbazole lead to a high power conversion efficiency with improved the short-circuit current due to hole mobility enhancement effect of carbazole unit.     

Synthesis and characterization of antioxidants and detergent dispersant based on some polyisobutylene copolymers

Polyisobutylene succinic anhydride-urea/polyamines (PIBSA) copolymers were synthesized as potential antioxidants and detergent dispersant agents for lubricating oils samples (SAE-30). Homogeneity, thermal stability and dispersancy of the solutions were determined. Fully soluble oil compounds that are thermally stable up to 250 °C were achieved. The oxidation stability of lube oil samples in the presence of four designed PIBSA additives (varying in the number of amine groups) was determined for a time period of up to 72 hours. The dependence of the additive efficiency on its concentration was studied to achieve maximum stability. Some PIBSA additives at concentration 3.0 · 10⁴ ppm exhibit the best results. Dispersivity values were measured at predetermined oxidation times. The results proved reliable dispersion capability as the nitrogen content of the additive is increased, i.e. the increase in the basic character of the additive leads to the increase in the neutralization capability. Moreover, the designed PIBSA additives retain their efficiency after long oxidation times, confirming their role as multifunctional nitrogen containing polymeric additive. Electronic Publication     

新型咔唑-吲哚并咔唑共轭聚合物材料的合成与性能研究

通过Suzuki偶联聚合方式合成了两种基于咔唑和吲哚并咔唑的新型共轭聚合物材料.目标聚合物具有较高的分子量,良好的热性能和电化学氧化还原性能.通过对材料的光物理性能分析,所制备的共轭聚合物材料是一类具有潜在应用价值的纯正蓝色电致发光材料.     

两种新型咔唑类双光子光聚合引发剂的合成与光学性质

报道了两种新型的咔唑类双光子光聚合引发剂,3,6-双[2-（4-吡啶基）乙烯基]-9-苯基咔唑（1） 和 3,6-双[2-（2-吡啶基）乙烯基]-9-苯基咔唑（2）,它们是通过钯催化的Heck偶连反应合成得到,并用元素分析,红外光谱,核磁共振氢谱和电喷雾电离质谱等对它们进行了全面的表征.这两个A-π-D-π-A结构的咔唑衍生物具有很好的单光子和双光子荧光行为,我们也详细研究了它们的溶剂效应和作为双光子引发剂用于微结构的制备,并讨论了它们的引发聚合的机理.     

Synthesis and characterization of amphiphilic star-shaped copolymers based on β-cyclodextrin for micelles drug delivery

Purpose: A series of β-CD amphiphilic star-shaped copolymers with exceptional characteristics were synthesized and their potential as carriers for micelles drug delivery was investigated.

Methods: A series of amphiphilic copolymers based on β-CD were synthesized by introducing poly (acrylic acid)-co-poly(methyl methacrylate)-poly (vinyl pyrrolidone) or poly (acrylic acid)-co-poly(methyl methacrylate)-co-poly(monoacylated-β-CD)-poly (vinyl pyrrolidone) blocks to the primary hydroxyl group positions of β-CD. The micellization behavior of the copolymers, the synthesis conditions, characteristics, drug release in vitro and tissue distribution of vinpocetine (VP) micelles in vivo were investigated.

Results: Around 60 types of β-CD amphiphilic star-shaped copolymers were successfully synthesized and the critical micelle concentration ranged from 9.80?×?10^?4 to 5.24?×?10^?2g/L. The particle size, drug loading and entrapment efficiency of VP-loaded β-CD-P₄ micelles prepared with optimal formulation were about 65?nm, 21.44?±?0.14%, and 49.05?±?0.36%, respectively. The particles had good sphericity. The cumulative release rates at 72?h of VP-loaded β-CD-P₄ micelles in pH 1.0, pH 4.5, pH 6.5, or pH 7.4 media were 93%, 69%, 49%, and 43%, respectively. And, the lung targeting efficiency of VP-loaded β-CD-P₄ micelles was 8.98 times higher than that of VP injection.

Conclusion: The VP-loaded β-CD-P₄ micelles exhibited controlled-release property, pH-induced feature and lung targeting capacity compared with VP injection, suggesting that the β-CD-P₄ copolymers are an excellent candidate for micelles drug delivery.     

荧光标记聚天冬氨酸的合成及性能

为实现聚天冬氨酸水处理剂浓度的准确快速检测,文中以聚琥珀酰亚胺、一乙醇胺、咔唑、环氧氯丙烷为主要原料合成了荧光标记聚天冬氨酸(Fluorescence Labeling Polyaspartic Acid,FLPASP)阻垢剂。通过红外光谱(IR)和核磁共振(1H-NMR)方法对各产物进行了结构表征;荧光光谱研究显示FLPASP具有很强的荧光强度,其水溶液质量浓度在阻垢剂使用浓度2mg/L~10mg/L范围内与荧光强度呈良好线性关系,而且水中常见垢源物质Ca2+和HCO-3对FLPASP的荧光强度无影响;静态阻垢试验表明,FLPASP具有优异的阻磷酸钙垢和良好的阻碳酸钙垢性能。     

Preparation and properties of alternating 2,7-linked carbazole copolymers with phenylene units with varying number of fluorine substituents

New alternating copolymers comprising 2,7-linked-3,6-dimethyl-9-(2-hexyldecy)-9H-carbazole and 1,4-phenylene units (P1), 2,5-difluoro-1,4-phenylene units (P2), and 2,3,5,6-tetrafluoro-1,4-phenylene units (P3) have been prepared using Suzuki cross-coupling conditions. The polymers were characterized by NMR spectroscopy, UV–vis absorption spectroscopy, fluorescence spectroscopy, and their weight-average molecular weights were estimated using gel permeation chromatography. The polymers are thermally stable up to 420 °C and display wide band gaps ranging from 3.16 to 3.2 eV. The polymers are electrolytically stable and emit around 400 nm. A discussion on the effect of the varying degree of fluorine substitution of the phenylene repeat units in polymers P1–P3 on their physical properties is presented.