1-烯丙基-3-甲基咪唑离子液体单体与丙烯腈共聚行为的研究

以1-烯丙基-3-甲基咪唑盐酸盐([AMIM]Cl)作为离子液体单体,偶氮二异丁腈作为引发剂,二甲基亚砜为溶剂,实现了与丙烯腈(AN)在不同反应条件下的自由基共聚合.研究了AN/[AMIM]Cl二元共聚合的动力学,得到了相应的竞聚率数据(rAN=8.11,r[AMIM]Cl=0).用1H-NMR、GPC、DSC、TGA等手段对共聚物进行了表征.通过对AN/[AMIM]Cl二元共聚及AN/IA/[AMIM]Cl三元共聚的研究发现,[AMIM]Cl在与丙烯腈共聚时具有双重作用,一部分离子单体进入到共聚物的分子链中调节其亲水性及可纺性,剩下的大部分留在纺丝液中可显著降低纺丝液的黏度,从而使高分子量高固含量纺丝液的纺制成为可能,有望得到高性能的碳纤维原丝.

Polymerization of 1,3-butadiene with VO(P-204)(2) and VO(P-507)(2) activated by alkylaluminum

The oxovanadium phosphonates (VO(P-204)(2) and VO(P-507)(2)) activated by various alkylaluminums (AlR3, R = Et, i-Bu, n-Oct; HAIR(2), R = Et, i-Bu) were examined in butadiene (Bd) polymerization. Both VO(P-204)(2) and VO(P-507)(2) showed higher activity than those of classical vanadium-based catalysts (e.g. VOCl3, V(acac)(3)). Among the examined catalysts, the VO(P-204)(2)/Al(Oct)(3) system (I) revealed the highest catalytic activity, giving the poly(Bd) bearing M-n of 3.76 x 10(4) g/mol, and M-w/M-n ratio of 2.9, when the [Al]/[V] molar ratio was 4.0 at 40 degrees C. The polymerization rate for I is of the first order with respect to the concentration of monomer. High thermal stability of I was found, since a fairly good catalytic activity was achieved even at 70 degrees C (polymer yield > 33%); the M-n value and M-w/M-n, ratio were independent of polymerization temperature in the range of 40-70 degrees C. By IR and DSC, the poly(Bd)s obtained had high 1,2-unit content (> 65%) with atactic configuration. The 1,2-unit content of the polymers obtained by I was nearly unchanged, regardless of variation of reaction conditions, i.e. [Al]/[V], ageing time, and reaction temperature, indicating the high stability of stereospecificity of the active sites.

Novel, highly efficient blue-emitting heteroleptic iridium(III) complexes based on fluorinated 1,3,4-oxadiazole: tuning to blue by dithiolate ancillary ligands

Novel blue-emitting phosphorescent iridium(III) complexes with fluorinated 1,3,4-oxadiazole derivatives as cyclometalated ligands and dithiolates as ancillary ligands have been synthesized and fully characterized; highly efficient OLEDs have been achieved using these complexes in the light-blue to blueemitting region.

Supramolecular architectures, photophysics, and electroluminescence of 1,3,4-oxadiazole-based iridium(III) complexes: From mu-dichloro bridged dimer to mononuclear complexes

One mu-dichloro bridged diiridium complex and three mononuclear iridium(III) complexes based on the 1,3,4-oxadiazole derivatives as cyclometalated ligands and acetylacetonate (acac) or dithiolates O,O'-diethyldithiophosphate (Et(2)dtp) or N,N'-diethyldithiocarbamate (Et(2)dtc) as ancillary ligands have been synthesized and systematically studied by X-ray diffraction analysis. The results reveal that three mononuclear complexes all adopt distorted octahedral coordination geometry around the iridium center by two chelating ligands with cis-C-C and trans-N-N dispositions, which have the same coordination mode as the diiridium dimer. The dinuclear complex crystallizes in the monoclinic system and space group C2/c, whereas three mononuclear iridium complexes are all triclinic system and space group P(1) over bar. In the stacking structure of the dimer, one-dimensional tape-like chains along the b-axis are formed by hydrogen bondings, which are strengthened by pi stacking interactions between phenyl rings of 1,3,4-oxadiazole ligands. Then these chains assemble a three-dimensional alternating peak and valley fused wave-shape structure. In each stacking structure of three mononuclear complexes, two molecules form a dimer by the C-H center dot center dot center dot O hydrogen bondings, and these dimers are connected by pi stacking interactions along the b-axis, constructing a zigzag chain.

White electroluminescence from a single-polymer system with simultaneous two-color emission: Polyfluorene as blue host and 2,1,3-benzothiadiazole derivatives as orange dopants on the side chain

Four single polymers with two kinds of attachment of orange chromophore to blue polymer host for white electroluminescence (EL) were designed. The effect of the side-chain attachment and main-chain attachment on the EL efficiencies of the resulting polymers was compared. The side-chain-type single polymers are found to exhibit more efficient white EL than that of the main-chain-type single polymers. Based on the side-chain-type white single polymer with 4-(4-alkyloxy-phenyl)-7-(4-diphenylamino-phenyl)-2,1,3-benzothiadiazoles as the orange-dopant unit and polyfluorene as the blue polymer host, white EL with simultaneous orange (lambda(max) = 545 nm) and blue emission (lambda(max) = 432 nm/460 nm) is realised. A single-layer device (indium tin oxide/poly(3,4-ethylenedioxythiophene)/polymer/Ca/Al) made of these polymers emits white light with the Commission Internationale de l'Eclairage coordinates of (0.30,0.40), possesses a turn-on voltage of 3.5 V, luminous efficiency of 10.66 cd A(-1), power efficiency of 6.68 lm W-1, and a maximum brightness of 21240 cd m(-2).

Green light-emitting polyfluorenes with improved color purity incorporated with 4,7-diphenyl-2,1,3-benzothiadiazole moieties

By incorporating 4,7-diphenyl- 2,1,3 benzothiadiazole instead of 2,1,3-benzothiadiazole into the backbone of polyfluorene, we developed a novel series of green light- emitting polymers with much improved color purity. Compared with the state-of-the-art green light-emitting polymer, poly(fluorene-co-benzothiadiazole) (lambda max = 537 nm), the resulting polymers (lambda(max) = 521 nm) showed 10-20 nm blueshifted electroluminescence (EL) spectra and greatly improved color purity because the insertion of two phenylene units between the 2,1,3-benzothiadiazole unit and the fluorene unit reduced the effective conjugation length in the vicinity of the 2,1,3-benzothiadiazole unit. As a result, the resulting polymers emitted pure green light with CIE coordinates of (0.29, 0.63), which are very close to (0.26, 0.65) of standard green emission demanded by the National Television System Committee (NTSC). Moreover, the insertion of the phenylene unit did not affect the photoluminescence (PL) and EL efficiencies of the resulting polymers. PL quantum efficiency in solid films up to 0.82 was demonstrated. Single-layer devices (ITO/PEDOT/ polymer/Ca/Al) of these polymers exhibited a turn-on voltage of 4.2 V, luminous efficiency of 5.96 cd A(-1) and power efficiency of 2.21 lm W-1. High EL efficiencies and good color purities made these polymers very promising for display applications.

成核剂1,3:2,4-二(亚苄基)-D山梨醇对PET/PEN共混体系结构和结晶形态影响

利用差示扫描量热仪、X射线衍射仪、正交偏光显微镜研究了成核剂 1,3 :2 ,4-二 (亚苄基 ) -D山梨醇(DBS)对聚对苯二甲酸乙二醇酯 (PET) /聚 2 ,6-萘二甲酸乙二醇酯 (PEN)共混体系的结构及结晶形态的影响。结果表明 :成核剂的加入 ,使PET/PEN共混体系熔融起始温度升高 10℃左右 ,结晶峰形变尖锐 ,说明加入成核剂后有效促进了PET/PEN共混体系的结晶。实验结果表明 :成核剂含量低于 1%时 ,PET/PEN共混体系晶体的球晶完整。成核剂含量大于 3 %时 ,PET/PEN /DBS共混体系晶体的球晶碎小。成核剂的加入 ,能够有效地减小球晶尺寸和降低球晶的完善性

1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5与中性磷(膦)萃取剂协同萃取镧B

研究了 1 苯基 3 甲基 4 苯甲酰基 -吡唑酮 5 (HPMBP)和中性有机磷 (膦 )类萃取剂Cyanex 4 71X(TIBPS ,B)在硝酸介质中对稀土元素La 的萃取 ,用斜率法和恒摩尔法探讨了萃取机理 ,确定了萃合物的组成为La(NO3 ) 2 ·PMBP·B ,计算了萃取平衡常数。比较了HPMBP与Cyanex 4 71X、Cyanex 92 1、Cyanex 92 3、Cyanex 92 5、DEH/EHP、P35 0及TBP的单独及混合体系萃取La 的性能 ,结果表明 :所有混合体系对La 均有协同效应 ,其中HPMBP与Cyanex 92 3、Cyanex 92 1、Cyanex 92 5的混合体系是萃取La 的有效体系。

Effect of La/Ce ratio on the structure and electrochemical characteristics of La0.7-xCexMg0.3Ni2.8Co0.5 (x=0. 1-0.5) hydrogen storage alloys

The effect of La/Ce ratio on the structure and electrochemical characteristics of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1, 0.2, 0.3, 0.4, 0.5) alloys has been studied systematically. The result of the Rietveld analyses shows that, except for small amount of impurity phases including LaNi and LaNi2, all these alloys mainly consist of two phases: the La(La, Mg)(2)Ni-9 phase with the rhombohedral PuNi3-type structure and the LaNi5 phase with the hexagonal CaCU5-type structure. The abundance of the La(La, Mg)(2)Ni-9 phase decreases with increasing cerium content whereas the LaNi5 phase increases with increasing Ce content, moreover, both the a and cell volumes of the two phases decrease with the increase of Ce content. The maximum discharge capacity decreases from 367.5 mAh g(-1) (x = 0.1) to 68.3 mAh g(-1) (x = 0.5) but the cycling life gradually improve. As the discharge current density is 1200 mA g(-1), the HRD increases from 55.4% (x = 0.1) to 67.5% (x = 0.3) and then decreases to 52.1% (x = 0.5). The cell volume reduction with increasing x is detrimental to hydrogen diffusion D and accordingly decreases the low temperature dischargeability of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1-0.5) alloy electrodes.

聚对苯二甲酸1,3-丙二醇酯溶液浇铸薄膜形态结构

聚对苯二甲酸 1 ,3-丙二醇酯 ( PTT)是典型的半结晶聚合物 ,从熔体结晶形成球晶 ,在某一结晶温度范围内 ,在球晶中可观察到环带结构[1～ 4 ] .一般认为 ,环带球晶的形成归因于片晶沿球晶径向的周期性扭曲[1,2 ] .本文研究了 PTT溶液浇铸薄膜在溶剂挥发过程中等温结晶的形态结构 .1　实验部分　　 PTT样品为美国壳牌化学公司产品 ,熔点为 2 2 8℃ .将 PTT粒料于 1 1 0℃溶解在苯酚和1 ,1 ,2 ,2 -四氯乙烷 (质量比为 60∶ 40 )的混合溶剂中 ,配成质量分数为 0 .2 %～ 2 %的溶液 ,滴少许溶液在加热的云母片上 ,在预先设定的结晶温度 ( 90～ 2 0 0℃ )下等温结晶 ,然后将 PTT薄膜快速冷却至室温 .用 Leica DMLP偏光显微镜 ( PL M)和 SPA- HV30 0原子力显微镜 ( AFM)进行形态表征 .2　结果与讨论　　图 1为 PTT溶液浇铸薄膜在不同温度下等温结晶后的 PLM图 ,可以清楚地看到 Maltese十字消光现象 .PTT溶液浇铸薄膜在 90～ 1 30℃的结晶温度范围内 ,形成环带球晶 ;当结晶温度为 1 40℃...

White electrolumineseence from a single-polymer system with simultaneous two-color emission: Polyfluorene as the blue host and a 2,1,3-benzothiadiazole derivative as the orange dopant on the main chain

New single-polymer electroluminescent systems containing two individual emission species - polyfluorenes as a blue host and 2,1,3-benzothiadiazole derivative units as an orange dopant on the main chain - have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue(lambda(max) = 421 nm/445 nm) and orange emission (lambda(max) = 564 nm)from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light-emitting diodes (PLEDs) based on the single-polymer systems has been investigated. The introduction of the highly efficient 4,7-bis(4-(N-phenyl-N-(4-methylphenyl)amino)phenyl)-2,1,3-benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single-layer device fabricated in air (indium tin oxide/poly(3,4-ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure-white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m(-2), luminance efficiency of 7.30 cd A(-1), and power efficiency of 3.34 lm W-1 can be obtained.

一种用高效液相色谱分析1,3-二氨基硫脲的方法

一种用高效液相色谱分析１，３－二氨基硫脲的方法，选取Ｚｏｒｂａｘ－ＯＤＳ为色谱柱担体，用甲醇和水配制成移动相，在高效液相色谱仪上用紫外多波长检测器进行检测，以色谱外标法进行定量。本发明具有产品分析仪器化；分析结果误差小；分析过程快速，方便易操作；不仅可以检测１，３－二氨基硫脲产品的纯度，还可用于检测含有微量１，３－二氨基硫脲的溶液及废液中１，３－二氨基硫脲的含量的优点。

Syntheses, structures and near-IR luminescent studies on ternary lanthanide (Er-III, Ho-III, Yb-III, Nd-III) complexes containing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate

The ligand Hhfth [4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dione], which contains a heptafluoropropyl group, has been used to synthesize several new ternary lanthanide complexes (Ln = Er, Ho, Yb, Nd) in which the synergistic ligand is 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy). The two series of complexes are [Ln(hfth)(3)phen] [abbreviated as (Ln)1, where Ln = Er, Ho, Yb] and [Ln(hfth)(3)bipy] [abbreviated as (Ln)2, where Ln = Er, Ho, Yb, Nd]. Members of the two series have been structurally characterized. The growth morphology, diffuse reflectance (DR) spectra, thermogravimetric analyses, and photophysical studies of these complexes are described in detail. After ligand-mediated excitation of the complexes, they all show the characteristic near-infrared (NIR) luminescence of the corresponding Ln(3+) ions (Ln = Er, Ho, Yb, Nd). This is attributed to efficient energy transfer from the ligands to the central Ln(3+) ions, i.e. an antenna effect. The heptafluorinated substituent in the main hfth sensitizer serves to reduce the degree of vibrational quenching. With these NIR-luminescent lanthanide complexes, the luminescent spectral region from 1300 to 1600 nm, which is of particular interest for telecommunication applications, can be covered completely.

Synthesis, structure, electrochemistry, photophysics and electroluminescence of 1,3,4-oxadiazole-based ortho-metalated iridium(III) complexes

Four new iridium(III) complexes 1-4, with 1,3,4-oxadiazole derivative as cyclometalated ligand for the first time, have been synthesized and structurally characterized by NMR, EA, MS and X-ray diffraction analysis (except 1). The stronger ligand field strength of the dithiolate ancillary ligands results in higher oxidation potentials and lower HOMO energy levels of complexes than acetylacetone. The absorption spectra of these complexes display low-energy metal-to-ligand charge transfer transition ranging from 350 to 500 nm. Complexes with dithiolate ancillary ligand emit at maximum wavelengths of ca. 500 nm, blue shifting 17 and 11 nm with respect to their counterpart with acetylacetone ligand. The electrophosphorescent devices with 2-4 as phosphorescent dopant in emitting layer have been fabricated. All devices have a low turn-on voltage in the range of 4.5 and 4.9 V. A high-efficiency green emission with maximum luminous efficiency of 5.28 cd/A at current density of 1.37 mA/cm(2) and a maximum brightness of 2592 cd/m(2) at 15.2 V has been achieved in device using 2 as emitter.