芳杂环二腈及其聚合物——Ⅹ.含苯并呋喃、苯并噻吩及喹啉环的二腈的合成及聚合

<正> 我们曾报道含不同苯并杂环二腈的合成、聚合及所得聚合物的热氧化稳定性。在这些二腈中与苯环相并的杂环皆含有二个杂原子。为了进一步阐明二腈的结构与聚合速度及所得聚合物热氧化稳定性的关系,本文合成了仅含一个杂原子与苯环相并的杂环化合物,即苯并呋喃、苯并噻吩及喹啉环的二腈(Ⅰ—Ⅲ)。     

芳杂环二腈及其聚合物——Ⅸ.4,4’-联苯二甲腈聚合动力学

本文研究了4,4′-联苯二甲腈在4,4′-联苯二甲腈氯化锌配合物催化下的聚合反应动力学,氰基浓度通过以铁氰化钾为内标的石腊糊法的红外光谱定量分析法测定。结果表明:该聚合反应是二级反应,聚合反应速度和氰基浓度及配合物浓度各成一次方比例。聚合反应表观活化能为12.4千卡/克分子。此外,也研究了不同的4,4′-联苯二甲腈金属氯化物配合物为催化剂对4,4′-联苯二甲腈聚合反应速度的影响,并对聚合反应机理进行了讨论。     

芳香族二腈的聚合

合成了三氯化硼、三氯化铝、四氯化钛、三氯化铁、氯化锌、氯化钴、四氯化锡、五氯化锑等八种氯化物和联苯二甲腈的分子复合物。它们具有一定的分子组成、熔点、 色泽、极易吸水分解。测定了它们的红外光谱,得到复合后氰基伸展振动频率的增加值及吸收峰强度增加值。这些复合物对联苯二甲腈的聚合有不同程度的催化能力。实验证明Lewis酸作为芳香族二腈聚合的催化剂是通过的腈生成复合物的形式进行催化的。     

芳杂环二腈及其聚合物——Ⅻ.二(对氰基苯基)醚和二(对氰基苯基)砜的聚合反应动力学

<正> 我们曾研究了4,4'-联苯二甲腈(I)在联苯二甲腈氯化锌配合物催化下的聚合反应动力学,结果表明,该聚合反应是二级反应,聚合反应速度与氰基和配合物的浓度各成一次方比例,可用下式表示:     

芳杂环二腈及其聚合物——Ⅷ.联苯二甲腈与金属氯化物的分子配合物

腈类化合物由于氮原子具有孤电子对,它可以和很多含有空轨道的金属卤化物配位生成分子配合物。Walton曾对乙腈、苯甲腈等腈类化合物与一些金属卤化物的分子配合物作过综述。文献亦曾报道脂肪族二腈与金属卤化物能形成配合物,而芳香族二腈和金属卤化物生成分子配合物则未见文献报道。此外,芳香族二腈在某些金属氯化物Lewis酸存在下,于300℃左右能进行聚合。为了探讨芳香族二腈在这些Lewis酸     

AROMATIC AND HETEROCYCLIC DINITRILES AND THEIR POLYMERS ⅩⅢ. POLYMERIZATION KINETICS OF BENZONITRILE AND THE STRUCTURE OF PRODUCTS

The polymerization kinetics of benzonitrile were studied, and the formation rate constants of s-triazine structure and linear polymer were determined. The influence of polymerization temperature and the amount of zinc chloride as catalyst on the ratio of linear to cyclic structure were also investigated, and the obtained results were discussed.     

THE AROMATIC AND HETEROCYCLIC DINITRILES AND THEIR POLYMERS. Ⅸ. THE POLYMERIZATION KINETICS OF 4, 4''-BIPHENYLDICARBONITRILE*

The polymerization kinetics of 4,4'-biphenyldicarbonitrile catalyzed by complex of 4,4'-biphenyl-dicarbonitrile with ZnCl_2 was studied. The cyano group concentration was measured by infrared spectroscopic analysis using potassium ferricyanide as the internal reference. The results proved that the polymerization is a second order reaction, and the activation energy of polymerization is 12.4 kcal/mol. The polymerization rates of 4,4'-biphenyldicarbonitrile catalyzed by other seven complexes were also measured. The polymerization mechanism was discussed.     

水凝胶纳米粒及其在生物医药领域的应用

作为环境响应性和纳米控释给药系统，水凝胶纳米粒主要用于毒副作用大、生物半衰期短、易被生物酶降解的多肽类、蛋白质等生物大分子药物的给药，在生物医药领域具有越来越广阔的应用前景。本文主要综述了水凝胶纳米粒的分类、制备方法及其在生物医药领域的应用。     

AROMATIC AND HETEROCYCLIC DINITRILES AND THEIR POLYMERS. Ⅺ. STUDY ON THE POLYMERIZATION OF AROMATIC AND HETEROCYCLIC DINITRILES BY INFRARED SPECTROSCOPY*

The polymerization rates of fourteen aromatic and heterocyclic dinitriles were measured by infraredspectroscopy and compared with that of 4, 4′-biphenyldicarbonitrile. The rate is greatly enhancedwhen an electron withdrawing group is substituted at the para position of cyano group in aromaticdinitriles. The polymerization rates of heterocyclic dinitriles wer discussed in terms of π-lectrondensity of the heterocyclic rings.