尼龙66/乙烯-醋酸乙烯酯共聚物接枝马来酸酐共混体系的研究(Ⅰ)乙烯-醋酸乙烯酯共聚物熔融接枝马来酸酐的制备与表征

以马来酸酐为单体、过氧化物为引发剂，采用熔融挤出法制备了乙烯-醋酸乙烯酯共聚物接枝马来酸酐(EVA-g-MAH)。重点讨论了不同型号的EVA、过氧化物引发剂品种及用量、单体MAH用量和加工工艺条件等因素时接枝反应的影响。通过化学滴定法和傅立叶红外光谱法(FTlR)证实部分马来酸酐确实以化学键连接到EVA分子链上。与聚乙烯(PE)、聚丙烯(PP)相比，EVA中由于含有醋酸乙烯(VA)基团，极性较大，与MAH的相客性较好，因而在相同的条件下接枝效率也更大；而且VA含量越大，越有利于接枝反应。比较不同的过氧化物引发剂BPO和DCP。发现DCP的引发效果更好。实验结果还表明，在EVA进行接枝反应的同时存在着交联反应，引发剂DCP的用量不宜过高，为得到接枝率适中，交联度很小的接枝产物，还要选择合适的MAH与DCP的用量。     

新型染料中间体手性胍的合成及表征

本文以(R)-苯基甘氨酸甲酯盐为原料合成了手性胍—化合物(6),并对合成反应条件进行了探索和优化。化合物(6)上与氮相连的活泼氢原子,可能对某些反应有不利影响,故用碘甲烷对其进行甲基取代,得到了新的手性胍—化合物(7),并做了表征。     

噻吩类导电高聚物的研究进展

噻吩类聚合物是研究较为广泛的功能高分子材料。详述了通过化学氧化聚合法和电化学氧化聚合法所合成的噻吩类导电聚合物的性能和用途,常用的结构与性能表征方法以及噻吩类导电聚合物在光、电、磁等各种领域中的应用。     

Structural characterization of Ti centres in Ti-silicalite and reaction mechanisms in cyclohexanone ammoximation

The main results obtained by means of many physical methods (IR, Raman, UV-Vis and XAFS spectroscopies) concerning the structure of the Ti centre in titanium silicalite and the reaction intermediates in the ammoximation of cyclohexanone are concisely reviewed.

The Ti is in tetrahedral coordination in vacuo and expands its coordination sphere upon interaction with adsorbates. In the presence of H₂O and H₂O/H₂O₂ solutions one of the SiOTi bridges is hydrolyzed with formation of (SiO)₃L₂TiOH (LH₂O) and (SiO)₃L₂TiOOH species, respectively. When NH₃ is dosed on (SiO)₃L₂TiOOH structures (SiO)₃L₂TiOO⁻NH₄⁺ species are formed. These species are thought to play an important role in the ammoximation reaction. The geometries of the peroxidic species (open or bridged) are discussed also on the basis of ab initio calculations.     

Classification of vegetable oils by high-resolution <Superscript>13</Superscript>C NMR spectroscopy using chromatographically obtained oil fractions

¹³C NMR spectra of oil fractions obtained chromatographically from 109 vegetable oils were obtained and analyzed to evaluate the potential use of those fractions in the classification of vegetable oils and to compare the results with the NMR analysis of complete oils. The oils included the following: virgin olive oils from different cultivars and regions of Europe and north Africa; “lampante” olive, refined olive, refined olive pomace, hazelnut, rapeseed, high-oleic sunflower, corn, grapeseed, soybean, and sunflower oils; and mixtures of virgin olive oils from different geographical origins. Oils were divided into two sets of samples. The training set (98 samples) was employed to select the variables that resulted in significant discrimination among the different oil classes. By using stepwise discriminant analysis, more than 98% of correct validated assignments were obtained; these results were confirmed when applied to the test set (11 blind samples). Results suggest that the use of oil fractions considerably increases the discriminating power of NMR in the analysis of vegetable oils.     

基于二氨基苯基卟啉的新型聚酰亚胺的合成与表征

卟啉类化合物的结构特征使其在很多领域受到广泛的关注,现在通常在卟啉上做修饰以获得更优的性能。以氨基苯基取代的卟啉化合物作为二胺单体和均苯四甲酸二酐为二酐单体,以苯甲酸为溶剂,通过反应合成粗产品新型的聚酰亚胺材料,用丙酮和氯仿洗涤得到纯产品,并进一步合成了Zn-卟啉聚酰亚胺。采用傅里叶红外吸收光谱、紫外-可见吸收光谱对产物进行了结构表征,对主要的紫外光谱、红外光谱吸收带进行了经验归属,以及原料与产物的对比分析,初步确定了合成产物的结构。结果表明,聚合产物是以卟啉骨架结构为主要聚合单元的聚酰亚胺类共聚物。     

钴卟啉三嗪类化合物的合成与表征

以单羟基苯基钴卟啉与三聚氯氰为原料,通过亲核取代反应合成了钴卟啉的三嗪类化合物,以硅胶为固定相,二氯甲烷为洗脱剂采用柱层析的方法对产物进行分离和提纯。最后采用紫外可见光谱、红外光谱等手段对合成产物进行了结构表征,对主要的紫外光谱、红外光谱吸收带进行了经验归属,初步确定了合成产物的结构。     

有机硅改性聚氨酯预聚体的制备及表征

以聚己二酸乙二醇酯、甲苯-2．4二异氰酸酯、二元醇、羟基硅油为主要原料,合成有机硅改性聚氨酯密封剂预聚体。用红外光谱法对其结构进行表征,同时测定预聚体的物理性能。结果表明．合成的聚氨酯密封剂预聚体受环境温度、空气湿度影响小,存放时间长,因此提高了密封胶力学性能。     

3，4-二氢吡咯[2，1-c][1，4]噘嗪-1-酮及其7-芳酰基衍生物的设计与合成

以2-吡咯基三氯乙酮为主要原料,经过乙二醇单酯化、羟基氯取代、环合三步反应制得了3,4-二氢吡咯[2,1-c][1,4]噁嗪-1-酮;又经过Friedel—Crafts酰基化和环合反应制得了未见文献报道的7-芳酰基-3,4-二氢吡咯[2,1-c][1,4]噁嗪-1-酮它们及其某些重要中间体的结构分别采用红外光谱、质谱、核磁共振氢谱、核磁共振碳谱以及高分辨率质谱进行了表征．