高热稳定性和可逆交联性质的含新型偶氮发色团电光聚合物的研究(英文)

制备了两种新型的分别含有以三苯胺为电子给体的偶氮类发色团作为特征活性官能团和3-呋喃甲酸及受保护的马来酰亚胺的可交联型聚合物体系.通过研究表明利用该制备方法,发色团在聚合物中的含量得到了极大的提高,分别达到32 .1 %( NLO1-P1)和44 .4 %( NLO1-P2) .该聚合物体系以"Diels-Alder"[4 +2]环加成反应作为其交联特征,具有高温非交联、低温交联的特点,其过程与以往的热交联型聚合物相反,可解决传统电光交联聚合物中存在的热交联对极化效率影响的问题并用热失重分析法(TGA)和差示扫描量热法(DSC)分析了这一过程.此外DA交联型聚合物,不需要引入额外的助交联剂,克服了传统热交联聚合物分离难的问题,最大程度的保证了材料的纯度.     

铒镱共掺磷酸镧纳晶的合成和近红外荧光性质

以磷酸三丁酯作为配体,使用高温溶液法合成了掺铒磷酸镧纳米晶体,高分辨电镜和XRD结果表明产物尺寸均一,直径4nm左右,具有高度的结晶性,在甲苯等有机溶剂中分散性良好.近红外发光光谱表明,产物在1535 nm处有发光峰,半高全宽为50 nm,高于目前掺铒光纤放大器(EDFA)的增益带宽.通过IR、元素分析研究发现,使用真空干燥等方法不能有效去除纳晶表面的羟基.为了进一步消除表面缺陷和猝灭基团对纳晶发光性质的影响,我们尝试在其外围生长一层LaPO₄壳做成核壳粒子以消除表面缺陷和隔离猝灭基团,结果表明,新的纳晶的发光强度得到了显著提高.     

一个对称萘酞菁的LB膜及其二阶非线性光学性质的研究

用水平提拉法制备了四叔丁基萘酞菁锌的LB膜。利用表面压-面积曲线、紫外-可见吸收光谱、小角X-射线衍射等表征了LB膜的结构,结果表明该化合物可以形成较高质量的具有很好层状结构的多层LB膜,在膜中分子大环平面垂直于基片平面并且以分子平面并不完全重合的H-聚集体存在。采用透射SHG方法测量了相应LB膜的二阶非线性光学性质,结果显示在实验条件下该化合物LB膜的宏观二阶非线性系数以及分子超极化率分别为X     

一种合成平面双核金属酞菁的新方法

A new planar binuclear bisphthalocyaninato-metal-planar hexa-tert-butylbisphthalocyaninato dicobalt (Ⅱ) was synthesized by the reaction of 4-tert-butylphthalic anhydride with pyromellitic dianhydride, urea and CoCl₂·6H₂O. This is a new synthesis method (phthalic route). The total yield reaches up to 15%. The synthetic reaction conditions are as follows: appropriate molar ratio of the reactant, reaction in solid phase and without ammonium molybdate as catalyst.     

新型偶氮化合物光致变色的研究

具有光致变色现象的有机化合物近年来一直为世人所关注.这是因为此类化合物在光信息存储材料方面具有潜在的应用价值.偶氮化合物作为一类重要的染料,已广泛地被人们从温度、溶剂、及光照波长等许多方面进行过研究^[1-3].     

MECHANISM OF PHOTOSENSITIZED OXYGENATION OF OLEFINS (Ⅰ) ——QUANTUM CHEMICAL STUDIES OF THE MECHANISM OF 1,2-CYCLOADDITIONS OF SINGLET MOLECULAR OXYGEN TO ELECTRON-RICH OLEFINS

In this paper, we studied in detail the mechanism of 1,2-cycloadditions of the first excited singletoxygen (O_2(~1Δ_g)) to aminoethylene and ethylene by semi-empirical and ab initio calculations ofquantum chemistry. Firstly, the transition states of every elementary process for the above two reac-tion systems were optimized by MINDO/3 attached by Powell method. The results calculated are dif-ferent from those obtained by others. Then we calculated the total reaction paths of the above tworeaction systems using Fukui's IRC theory. The results calculated not only affirm the reliability ofthese transition states calculated by us, but also prove that the reactions of electron-rich olefins withO_2(~1Δ_g) proceed indeed via a zwitterion intermediate. According to these, we explain reasonablythe electronic effects of the substituents.     

烯烃光敏氧化反应机理——Ⅰ.富电子烯烃与单线态氧1,2-加成反应机理的量子化学研究

本文用量子化学(简称量化)的半经验及从头算法对氨基乙烯及乙烯与单线态氧1,2-加成反应机理进行了研究。首先应用MINDO/3辅以Powell法对两个体系各基元过程过渡态进行了优化。得到了与前人不同的结构。而后利用Fukui提出的IRC理论计算了这两个体系整个反应途径。计算结果不但证实我们所得过渡态结构的可靠性,也证实对于富电子烯烃,反应确实经由两性离子中间体。同时基于反应途径对反应全过程进行了详细分析并结合从头算相互作用能的分解对取代基电子效应提出了较为深入合理的理论解释。     

THEORETICAL STUDY ON THE 1,4-CYCLO-ADDITION REACTION BETWEEN SINGLET OXYGEN (~(1)O_(2)) AND IMIDAZOLE

Quantum chemical ab initio method has been used to study the cycloaddition reaction between singlet oxygen and imidazole theoretically. The intermediate product, an endoper-oxide, of which the structure has not yet been found experimentally was optimized by using energy gradient method. The transition state (TS) structure of this reaction was also located on the potential energy surface and characterized. From the structural features of the TS, e.g. the transition vector of the imaginary vibration mode, as well as the interaction of orbitals, it is realized that this cycloaddition is a synchronous concerted reaction. The activation barriers calculated are 69.5 kJ·mol (forward reaction) and 140.4 kJ·mol-1 (backward reaction) respectively (6-31G results).     

耐热性有机高分子的性能研究及其在塑料光纤中的应用

本文以N 环乙基马来酰亚胺 (CHMI)和甲基丙烯酸甲酯 (MMA)共聚得耐热性透明材料 ,讨论了共聚产物的透明性和玻璃化温度与CHMI含量的关系 .以上述材料为基础 ,应用界面凝胶法制备光纤预制棒 ,在探讨了CHMI和PCHMI的折射率的基础上 ,分析并测试了光纤预制棒的折射率分布 ,最后拉制成塑料光纤 (GI POF)并测试了光纤的光透射窗口     

贵金属新分析势能面及在金属表面计算机模拟中的应用

导出了一组贵金属:铜、银、金晶体新的分析势能面. 新导出的分析势能面不仅精确地描述了该族金属元素晶体的宏观性质,如:弹性模量、声子色散曲线、原子化能、表面能等,也给出这些金属表面性质正确的描述. 利用新分析势能面对贵金属晶体表面性质进行了计算机模拟,模拟结果与实验数据十分吻合.