一些氮氧自由基和受阻胺化合物对单重态氧的猝灭能力及其与光稳定作用的关系

本工作测定了一系列稳定氟氧自由基( )化合物及一些受阻胺光稳定剂对单重态氧(¹O₂)的猝灭速率常数(k_q^1O₂),发现不同结构的 对¹O₂的猝灭能力很接近,但它们对聚丙烯(PP)膜的光稳定作用却相差很大。四甲基哌啶醇(TMP)及其衍生物对¹O₂的猝灭能力远不如相应的五甲基哌啶醇(PMP)及其衍生物,但前者对PP的光稳定能力却胜于后者。这说明在对聚合物的光稳定作用中, 和受阻胺光稳定剂对¹O₂的粹灭作用不占重要地位,也说明¹O₂在PP的光氧化过程中很可能不是主要因素。     

远程“传染”对聚丙烯光氧老化的影响

研究了聚丙烯(PP)在附近有其他聚合物存在下,其光氧老化受"传染"的现象.研究发现,PP的光氧化会受到邻近聚合物降解产物的影响而被加速,即发生光氧化降解的"传染".当"传染源"不同时,被"传染"的情况也有所不同.在PP、聚甲基丙烯酸甲酯(PMMA)、尼龙6(PA6)和苯乙烯-丙烯酸酯共聚物(PSB)中,PSB的降解产物影响最大,使得PP光氧化的降解速率成倍增长.老化后的PP或PMMA作为"传染源"时,对PP的光氧化降解速率有进一步的促进.这种"传染"行为与聚合物降解产物的种类和含量有很大的关系.     

FeCl2-K2MoS4体系电催化还原乙炔为乙烯

采用控电位电解、循环伏安法和交流阻抗法研究了FeCl₂-K₂MoS₄体系对乙炔在石墨电极上还原为乙烯的电催化活性及反应机理。实验结果表明,当石墨阴极的电位控制在-1.50V(vs.SCE)时,FeCl₂+K₂MoS₄的DMF溶液对C₂H₂还原为C₂H₄表现出明显的电催化活性和高的选择性。在-0.5～-1.0V时Mo(Ⅵ)还原为Mo(Ⅴ);在按连串的电子传递机理进行的Mo(Ⅴ)→Mo(Ⅲ)反应的电位区间(-1.0～-1.50V)溶液中所形成的络合品种传递电子的能力更强。Mo(Ⅲ)可能是络合物的电活性成分。     

竹红菌素自敏光氧化反应机制的研究

本文对竹红菌素自敏光氧化反应的机制作了较详细的研究,竹红菌素通过自敏光氧化反应生成不稳定的过氧化物,它可以放出¹O₂回到母体化合物,也可以转化为稳定的氧化产物,我们用活泼的单重态氧的接受体捕获到了体系中放出的¹O₂,用吸收光谱的变化证明过氧化物回到了母体化合物。文中还用猝灭实验证实此自敏光氧化反应除涉及¹O₂机制外,还有其它机制起着作用。     

以十二烷基苯磺酸钠为模型反应物的Y2O3/TiO2复合催化剂的制备及光降解催化性能

采用浸渍法制备了Y₂O₃/TiO₂复合氧化物催化剂,并用紫外可见光谱、SEM、BET等手段对其进行了表征.以水相十二烷基苯磺酸钠(DBS)溶液的光催化降解反应为实验模型,考察了TiO₂掺杂Y₂O₃后的光催化氧化活性,并探讨了Y₂O₃掺杂量、吸附性、焙烧温度及时间对Y₂O₃/TiO₂复合氧化物催化剂光催化活性的影响.实验结果表明:复合氧化物催化剂Y₂O₃/TiO₂存在某一最佳组分比值,当两者重量比为1:200时,其催化活性是同样条件下前体催化剂TiO₂的2.4倍.     

9,10-二氰基蒽敏化光氧化反应的溶剂效应

本文通过α,β-蒎烯及1,4-二苯基-1,3-丁二烯的9,10-二氰基蒽(DCA)敏化光氧化反应在一系列溶剂中产物生成的相对量子效率及单线态氧(¹O₂)产物的含量,对β-蒎烯在乙腈中的反应动力学分析,讨论了反应的溶剂效应,证明了DCA敏化光氧化反应,包括¹O₂产物都是经由电子转移的反应机理。     

含长丙烯序列无规乙丙共聚物的合成与表征

用δ-TiCl₃-Et₂AlCl催化剂,以庚烷作溶剂,在单体C₃含量>60mol%的情况下,乙丙常压共聚可得到含长丙烯序列无规乙丙共聚物(LP-EPR)。其特性粘数〔η〕在2—3dl/g之间。影响〔η〕的主要因素是〔Al〕/〔Ti〕比、聚合温度和时间。共聚物的组成主要依赖单体C₃含量。通过庚烷萃取、红外、扭摆、x-射线衍射及相差显微镜等方法证明,在共聚物的无规乙丙分子链中含有全同聚丙烯(PP)序列,序列含量直接影响共聚物的结晶度、强度和硬度。     

二乙基硫醚光敏化氧化反应动力学的研究

本工作以高分子化的孟加拉玫瑰为单线态氧敏化剂,对二乙基硫醚光氧化为二乙基亚砜的反应进行了研究。通过稳态处理,得到了光氧化反应的动力学公式。实验证明,存在着与上述公式相符的下列关系式: R_Ox=K[R₂S]⁰[O₂]^0.42[I]     

PP-SBS共混物光氧化降解的研究

和橡胶类树脂进行共混是聚丙烯(PP)改性的重要途径之一,共混有橡胶组分的PP改性树脂在其力学性能获得改进的同时,其老化性能必然也有一定的变化,我们用红外光谱方法研究了聚丙烯和苯乙烯-丁二烯星型嵌段共聚物的共混物(PP-SBS)的光氧化降解行为。     

用表面处理法降低TiO2粉末光活性问题的研究

本工作采用了两种简便的方法即用不同金属盐和金属氧化物对两种晶型(锐钛矿型和金虹石型)TiO₂粉末进行表面处理来降低TiO₂的光活性并对两种表面处理方法的优缺点作了比较,在评价TiO₂光活性时采用异丙醇光氧化反应的方法。实验证明,用金属盐表面处理TiO₂,其光活性有明显降低。用金属氧化物对TiO₂进行表面处理,在氧化物/TiO₂比例适当时也可以得到与金属盐表面处理TiO₂的同样效果。此外,我们还对TiO₂表面处理后能降低其光活性的作用机制问题进行了讨论。     

Temperature-dependent structural changes of[Bmim]FeCl4 magnetic ionic liquid characterized by an in-situ X-ray absorption fine structure

The temperature-dependent structural changes in 1-butyl-3-methylimidazolium tetrafluoride([Bmim]FeCl4)magnetic ionic liquid(MIL)were investigated by using in-situ X-ray absorption fine structure(XAFS)combined with Raman spectroscopy and DFT calculations.XAFS re sults revealed that the coordination number and bond length of Fe-Cl in the anion of[Bmim]FeCl4 MIL decreased with increments in temperature.These results directly reflected the dissociation of tetrahedral structure[FeCl4]^-,and the formation of bridge-chain[Fe2 Cl5]^+,and[FeCl2]^+species in the anion of[Bmim]FeCl4 MIL.These behaviors indicated that[FeCl4]^-dissociation was endothermic,and was promoted by increased temperature.The results obtained through XAFS were in agreement with those obtained through Raman spectroscopy and DFT calculations.     

三氟甲烷磺酸稀土盐对聚丙烯热稳定性的影响及机理

通过熔融共混将三氟甲烷磺酸镱[Yb(OTf)₃]和三氟甲烷磺酸镧[La(OTf)₃]添加至聚丙烯(PP)中, 制得PP/Yb和PP/La材料, 并对其热稳定性进行表征. 热失重分析(TGA)和差示扫描量热分析(DSC)结果显示, Yb(OTf)₃和La(OTf)₃均可以显著提高聚丙烯的热稳定性. 当Yb(OTf)₃添加量仅为1%(质量分数)时, PP的起始分解温度从275 ℃提高至305 ℃, 最大分解温度从384 ℃提高至405 ℃, 160 ℃下的氧化诱导时间从12.1 min延长至43.0 min, 热焓从1907 J/g降低至483 J/g; 而PP/La1的起始分解温度、 最大分解温度、 160 ℃下的氧化诱导时间和热焓分别为300 ℃, 409 ℃, 18.6 min和633 J/g. 结果表明, La(OTf)₃对聚丙烯热稳定性的改善作用弱于Yb(OTf)₃, 对2种稀土盐产生不同实验结果的原因进行分析并提出机制. 由于阴离子和阳离子的共同作用, Yb(OTf)₃和La(OTf)₃均可提高PP的热氧稳定性. La(OTf)₃中三氟甲烷磺酸根的自由基捕捉能力和稀土离子的配位能力发挥主要作用, 而Yb(OTf)₃中的稀土离子的高反应活性也起到关键作用.     

Extractive desulfurization of fuel oil with metal-based ionic liquids

Several metal-based ionic liquids (ILs) were synthesized and used as extractants for the desulfurization of dibenzothiophene (DBT) in simulated fuel oil. The effects of several anion and metal ions, n(ILs)/n(metal) as mole ratio, V_IL/V_oil and extractive times on the removal ratio of DBT were investigated in detail. The results showed that [BMIM]HSO₄/FeCl₃(BMIM was short for 1-butyl-3-methyl imidazole) was superior to the other ILs for the extractive desulfurization. A total of 100% of DBT was removed at room temperature in 5 min with V_[BMIM]HSO₄=FeCl₃=V_oil=1:1. The extractive activity of [BMIM]HSO₄/FeCl₃ IL did not change almost after five runs. Extractive desulfurization of different sulfur compounds and commercial diesel fuel oil were also examined. The removal ratios of the sulfur compounds as the reaction substrates were all over 90% and the sulfur content of commercial diesel oil decreased to 120 ppm from 12,400 ppm.     

氢氧化铁溶胶制备条件对其电泳等性能的影响

In order to explore the optimum preparation conditions, effects of FeCl₃ dosage, hydrolysis temperature and dialysis time on the particle size, conductivity, pH and double layer potential (ζ) of Fe(OH)₃ sol were systematically studied. The ultraviolet-visible reflection spectrophotometry was used to track the particle size of Fe(OH)₃ sol. With the increase of FeCl₃ dosage, the particle size of the colloid increased, the reflectivity decreased and the reflection wavelength shifted to longer wavelength, which is in accordance with the quantum confinement effect theory. The excessive Cl^- would inhibit the conductivity, and the stability of Fe(OH)₃ sol with larger particle size would be worse. Because of the better synergistic effect of q/m and V/l under the action of electric field of 80 V with electrophoresis, the ζ of the Fe(OH)₃ sol prepared under the optimum conditions (c_FeCl3, 0.01 mol·L^-1; 100℃; dialysis time, 1 d) was 43.67 mV which was most close to the theoretical value of 44.00 mV.     

Anisotropic conductivity of undoped and [FeCl4]-doped trans-polyacetylene

EHMO/CO (crystal orbital) quantum chemical methods were used to calculate the two-dimensional (2D) energy band structures of highly oriented trans-polyacetylene (PA) undoped and doped with [FeCl₄]⁻. The band gaps (E_g) of undoped PA in directions parallel and perpendicular to the oriented direction were 1.195 and 3.040 eV, respectively, and that of doped PA with [FeCl₄]⁻ were 0.0223 and 0.0504 eV, respectively. Based on the calculational results, the changes in conductive properties from undoped PA to [FeCl₄]⁻ doped PA could be interpreted. The conductivity anisotropy ratio σ/σ decreased when PA was doped by [FeCl₄]⁻, because the PA chain and the dopant showed a strong interchain coupling. The theoretical results for undoped and doped PA were in good agreement with the experiment.     

Research on hydration of phenylacetylene assisted with additives in near-critical water

The hydration of phenylacetylene in near-critical water,assisted with additives（NaHSO₄,ZnCl₂,FeCl₃）,has been successfully conducted with temperature and residence time ranges of 220-300℃and 60-180 min,respectively.The results showed the catalytic ability is FeCl₃>ZnCl₂>NaHSO₄.The maximum yield of product acetophenone was 96.68%at 260℃,120 min.Based on the results found,a possible mechanism of hydration of phenylacetylene in near-critical water was proposed.     

ON THE QUENCHING OF SINGLET OXYGEN BY α-TOCOPHEROL

Abstract —D-α-tocopherol was found to be an effective quencher of ¹O₂ molecules ( k = 2.5 times 10⁸→mol^-1 s^-1 in pyridine) by measuring its effect on the autosensitized photooxidation of rubrene. The quenching process was shown to be almost entirely 'physical', that is, α-tocopherol deactivated about 120 ¹O₂ molecules before being destroyed. The results suggest that this process may be a mechanism for the protective effect of α - tocopherol in photodynamic action.     

一种新型室温固化、耐高温环氧树脂体系及其性能

采用1-己基-3-甲基咪唑四氯化铁盐([C₆mim]FeCl₄)与混合胺复配室温(20 ℃)固化双酚A型环氧树脂E-51,并与其它脂肪胺类室温固化E-51体系在力学性能、热性能、耐老化性能方面的数据进行了比较,同时分析了[C₆mim]FeCl₄不同添加量对固化体系性能的影响,结果显示:[C₆mim]FeCl₄/混合胺复配室温固化E-51体系的室温拉伸强度可达90 MPa,高温(120 ℃)下也保持了良好的力学性能,热失重(5%)分解温度为310 ℃,200 ℃老化7 d后,拉伸强度为28 MPa,是一种可在高温下使用的新型环氧树脂室温固化体系。     

Inhibition of photooxidation of iron(II) by some semiconductors

The photooxidation of iron(II) in aqueous ethanol is less in presence of TiO₂, ZrO₂, V₂O₅, CeO₂, ZnO, Fe₂O₃, CdO, PbO, SnO₂, CdS, ZnS and Al₂O₃ than in their absence. The photogeneration of iron(III) was studied at different [Fe²⁺], amounts of semiconductors suspended, airflow rates, light intensities, solvent compositions and wavelengths of illumination. The catalysts show sustainable photocatalytic activity. The metal oxides and sulfides reduce iron(III), formed by the homogeneous photooxidation of iron(II). TiO₂, CeO₂, ZnO, Fe₂O₃, CdO, PbO, SnO₂ and Al₂O₃ effectively suppress the photooxidation of iron(II); ZrO₂, ZnS and CdS also suppress but not completely. At high catalyst-loading V₂O₅ catalyses the photooxidation of iron(II). The mechanisms of the photocatalytic processes are discussed.     

3,3-双(N-辛基-2-甲基吲哚)邻苯二甲内酯荧烷在乙醇溶液中的显色性能

测试了3,3-双(N-辛基-2-甲基吲哚)邻苯二甲内酯荧烷(ck-16)在显色前后的¹³C NMR谱图,揭示了其显色前后的结构变化及其显色机理。 利用紫外可见吸收光谱法研究了ck-16在乙醇溶液中与不同显色剂作用后的光谱性质,测定了其与常用显色剂间的络合比和不稳定常数,并进一步研究了外界条件的改变对ck-16在乙醇溶液中与特定显色剂作用后显色性能的影响。 研究发现,亲电阳离子进攻ck-16荧烷分子的苯酞环,使苯酞环断裂,推电子的N原子和吸电子的羰基O原子之间建立π电子迁移通道使分子显色。 在乙醇介质中,ck-16与不同显色剂作用后具有不同的显色效果;对路易斯酸和有机弱酸这两类显色剂而言,ck-16与所测的四种显色剂(FeCl₃、草酸、CuCl₂、水杨酸)均以1:1的形式络合,ck-16与Fe³⁺的不稳定常数最小,结合最稳定,草酸其次,与Cu²⁺的相近,ck-16与水杨酸的结合最弱;在乙醇中,放置时间对ck-16/FeCl₃和ck-16/H₂C₂O₄两个体系的吸光度影响不大,但两体系表现出随水含量变化不同的敏感性,ck-16/FeCl₃体系具有比ck-16/H₂C₂O₄体系更为灵敏和快速的水致褪色性能。