1,3-双(N-取代苯氨基)方酸内鎓盐的合成

在方酸内鎓盐中,四碳环的电荷分离使其氧原子带部分负电荷,成为潜在的良好配位基。 据此,作者于前文中合成了以双苯氨基方酸内鎓盐为骨架、苯环的2—位对称引入多甘醇醚氧 链的多齿配体,并以它们为萃取剂或电活性物质成功地实现了水相中UO_2~(2 )的萃取及碱水中NH_3 的测定。如果配基链由苯环的2—位移至N上,整个配体分子的几何及电子结构将发生改变, 四碳环上的氧与侧链的匹配情况也将不同。此外,苯环上的取代基将可能通过共轭体系直接影响 四碳环上氧的电荷状态及配位能力。因此,本文合成并研究了一类新的1,3—双(N—取代苯氨基) 方酸内鎓盐型多齿配体2(a～h)(见下式)。     

乳液聚合共聚物玻璃化转变温度及其理论计算

从共聚单体的竞聚率、油相水相分布系数出发,通过动力学模拟计算了丙烯酸丁酯与醋酸乙烯酯乳液共聚物的链结构,并用Johnson公式对其玻璃化转变温度(T_g)进行了理论计算,给出了共聚物T_g及其对应聚合物的重量分布图。发现半连续共聚物有1个T_g,其值随共聚物组成而变化;但一步法共聚物有两个T_g:低温区T_g代表富丙烯酸丁酯共聚物,高温区T_g则代表PVA均聚物。计算结果与实验十分吻合。     

Imidazole Coordinated Sandwich-type Antimony Polyoxotungstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ）

The imidazole covalently coordinated sandwich-type heteropolymngstates Na9[ {Na（H=O2}3{M（C3H4N2）}3（ Sb W9O33）2]·xH=O（M=Ni^Ⅱ, Co^Ⅱ, Zn^Ⅱ, Mn^Ⅱ） were obtained by the reaction of Na2WO4·2H2O, SbCl3·6H2O, NiCl2·6H2O [MnSO4·H2O, Co（NO3）2·6H2O, ZnSO4·7H2O] and imidazole at pH≈7.5. The structure of Na9[{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2]·32H2O was determined by single crystal X-ray diffraction. Polyanion [{Na（H2O）2}3{Ni（C3H4N2）}3（SbW9O33）2}3]^9- has approximate C3v symmetry, imidazole coordinated six-nuclear duster [{Na（H2O）2}3{Ni（C3H4N2）}3]^9＋ is encapsulated between two （α-SbW9O33）^9-, the three rings of imidazole in the polyanion are perpendicular to the horizontal plane formed by six metals （Na-Ni-Na-Ni-Na-Ni） in the central belt, and x-stacking interactions exist between imidazoles of neighboring polyanions with dihedral angel of 60%. The compounds were also characterized by IR, UV-Vis spectra, TG and DSC, and the thermal decomposition mechanism of the four compounds was suggested by TG curves.     

溶胶-凝胶法制备还原态K-Co-Mo催化剂的合成醇性能

应用溶胶-凝胶法制备了还原态K-Co-Mo催化剂, 比较了不同的组分和不同的反应条件对合成醇性能的影响。实验结果表明，适量钾和钴助剂的添加能显著提高催化剂合成醇的性能，尤其是提高了C2+醇的选择性。此外，反应温度、压力以及空速对合成醇影响明显，升高温度可以提高催化反应中低碳醇的收率，但选择性下降；增加压力和空速可以提高低碳醇的收率和选择性，对合成低碳醇有利。在230 ℃，6.0 MPa，14 400 h－1条件下，催化剂合成低碳醇的收率为375.4 g/kg·h，选择性为70.2%，C1OH/C2+OH为0.48。     

氢部分选择性催化还原NO反应研究

在低钯含量活性非均布Pd/Al2O3催化剂上，实现了富氧条件下，氢部分选择性催化还原NO过程，低温、富氧条件下NO的转化率高达80％－100％。NO直接分解实验表明，600℃，NO分解转化率在无氧时为17．3％，有0．5％氧存在时接近于0。氢非选择性还原NO条件下，100℃以下，NO转化率为100％。根据实验结果及文献，推测了氢部分选择性还原NO过程中可能存在的反应，不同的反应温度下，NO脱除反应有所不同。在115℃以下，NO还原产物为NH3；115℃－155℃，NO还原产物为NH3、N2O和N2；155℃以上，NO还原产物中无NH3存在。NO还原反应与氢氧反应是平行的竞争反应。     

反相乳液聚合制备壳聚糖接枝共聚物及应用

以壳聚糖、丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵为原料,硝酸铈铵为引发剂,Span-20为乳化剂,通过反相乳液聚合技术,合成壳聚糖阳离子接枝共聚物。分析讨论了乳化剂用量、引发剂浓度、油水体积比、单体配比、反应时间、反应温度对共聚物接枝率的影响,并采用正交试验方法对合成条件进行了优化。研究了其对重金属离子Cu2 、Cd2 、Zn2 的吸附性能。结果表明,在Cu2 、Cd2 、Zn2 的混合离子体系中,该共聚物对Cu2 、Zn2 有选择性吸附。     

微波辐照下无皂阳离子聚(St-MMA)高分子纳米粒子的制备和表征

讨论了微波辐照下 ,以丙酮 水为分散介质 ,利用阳离子型自由基引发剂偶氮二异丁基脒盐酸盐(AIBA)引发苯乙烯 (St)和甲基丙烯酸甲酯 (MMA)共聚 ,合成出表面带正电荷的P(St MMA)共聚物纳米粒子 ,考察了丙酮用量、单体和引发剂浓度对纳米粒子粒径、粒径分布和乳液稳定性的影响 .结果表明 ,丙酮 水的体积比由 0增加到 1 2 6∶1时 ,粒子的平均水化半径从 12 2 2 1nm降低到 2 4 6 8nm ,粒径分布变宽 ,乳液抗电解质稳定性逐渐增强 ;增加引发剂和共聚单体MMA的浓度 ,粒子的水化半径逐渐减小 ,粒径分散系数增大 .     

Two New C—21 Steroidal Glycosides from Cynanchum aurichulatum

Two new C-21 steroidal glycosides, cynanauriculoside I and cynanauriculoside Ⅱ, were isolated from the roots of Cynanchum aurichulatum. Their structures were established using spectroscopic methods including one and two-dimensional NMR.     

金(Ⅲ)与杯[4]乙酯合钠(Ⅰ)超分子化合物: [Na(C60H80O12)]+[Au(SCN)4]-的合成、结构及性能

A novel super molecule [Na(C₆₀H₈₀O₁₂)]⁺[Au(SCN)₄]^- was obtained by extraction of calix[4] arene (L) for an aqueous solution containing [AuCl₄]^-, and NaCl into CH₂Cl₂. The crystal structure and properties of the title super molecule were characterized by single-crystal X-ray diffraction, IR and ¹H NMR spectra. The X-ray single crystal structure analysis shows that the crystal was Tetragonal system with space group P4/n and the unit cell parameters were as follows: a=2.880 8(18) nm, b=2.880 8(18) nm, c=2.292 4(5) nm, and final R indices [I>2σ(I)]: R₁=0.048 5, wR₂=0.106 1. CCDC: 243229.     

FTIR-ATR技术研究聚氨酯类文物保护材料的光降解

Polyurethanes are one kind of relic protection materials commonly used. During artificial photo-ageing, three polyurethanes, HDI-based polyurethane, MDI-based polyurethane and TDI-based polyurethane, have been considered to undergo UV radiation. Photochemical degradation of the polyurethanes has been monitored by means of Fourier transform infrared spectroscopy with attenuated total reflection accessory （FTIR-ATR）. It was proved that the mechanism of the photochemical degradation of polyurethanes might be the scissions of carbamate （urethane） groups and the re-reactions of radical groups formed in the scission reactions. From the experiment results HDI-based polyurethane, an aliphatic diisocyanate, could be considered to be more suitably used as relic protection materials among these three polyurethanes for its ageing products with less color.