螯合型高分子

由于现代技术,特别是高速飞行和火箭技术的特殊要求,耐高温高分子是近年来高分子领域中的一个主要研究课题。在具有潜在耐高温性能的各种类型高聚物中,以金属通过螯合方式作为主链的一部分的螯合高分子,或配位高分子,近来已引起广泛的注意。虽然至目前为止,所报导的螯合高分子,由于分子量太低和不熔,都还没有实用的价值,但许多研究工作者都还在继续努力。这是一个值得注意的新方向。     

共轭二烯烃的Ziegler─Natta催化聚合

共轭二烯烃的聚合是配位阴离子聚合，双金属配合物是聚合的活性中心，控制单体的构象是控制聚合物结构的关键。单体在低值配位场稳定化能（ＬＦＳＥ）过渡金属离子，如Ｃｏ~（２＋）、Ｔｉ~（３＋）上螯合，螯合单体具有顺式构象，所得聚合物具有顺１，４结构；在中等ＬＦＳＥ的过渡金属离子，如Ｖ~（３＋）、Ｃｒ~（３＋）上配位，配位单体具有反式构象，所得聚合物具有反１，４结构或是１，２聚合物；高ＬＦＳＥ值过渡金属离子不易控制活性价态，双金属配合物不够稳定，所得聚合物分子量常较低，结构规整性也常不够理想。     

咪唑代聚环氧氯丙烷-铜络合物的合成及其对2,6-二甲基苯酚氧化偶合的催化作用

本文以二甲基亚砜为溶剂,通过大分子反应,由环氧氯丙烷(PE)和咪唑锂合成了咪唑代聚环氧氯丙烷(PEIm)。此聚合物的铜络合物[PEIm-Cu(Ⅱ)]主要是4个咪唑基团与1个Cu(Ⅱ)配位的形式。在取代度α为30—55％范围内,PEIm—Cu(Ⅱ)为不溶的固体,对2,6-二甲基苯酚氧化偶合反应具有明显的催化活性,反应中显示“协同效应”、“底物抑制”等酶催化的一些特点。     

EFFECTS OF CONFORMATION OF POLYMER LIGANDS IN COPPER(Ⅱ) COMPLEXES ON CATALYLIC ACTIVITIES AND MECHANISM OF OXIDATIVE COUPLING OF β-NAPHTHOL

Copper(Ⅱ) complexes of sericin, chitosan, 6-and 2-aminodeoxystarch were used as catalysts in oxidative coupling of β-naphthol, the effects of conformation of the polymer ligands in these complexes on activities of the catalysts and mechanisms of the reaction were studied. It was found that if the catalysts react with the substrate by mechanism similar to the enzymic catalysis they must be composed of polymer ligands with highly coiled, especially with densely helicoidal, conformations. While catalysts composed of loosely coiled or helicoidal hgands react with the substrate through molecular collision and have relatively lower activities only. Under nitrogen, catalysts from sericin and chitosam reacting with β-naphthol give optically active β-binaphthol, rotating polarized light to right, but the stereoselectivities are rather low.     

EFFECTS OF SOLVENT POLARITY ON FREE RADICAL COPOLY MERIZATION OF 5-HEXENOIC ACID AND ACRYLONITRILE

The effects of solvent polarity on free radical copolymerization of 5-hexenoie acid and acrylonitrile at 60℃ were studied. It was observed thatas the polarity of solvents enhanced, both the copolymcrization rate and the reactivity ratios r_1, r_2 increased, while the alternating tendency of monomer units in copolymer chain decreased. It is believed that the solvent polarity raises the reactivities of acrylonitrile monomer and its growing chain radical, but causes no distinct variation in those of 5-hexenoic acid.     

用裂解气相色谱法进行聚氯乙烯一-红泥塑料的结构表征

用裂解气相色谱法(PGC)进行了聚氯乙烯—红泥塑料(PVC—RM)的结构表征。研究了聚氯乙烯(PVC) 和PVC—RM经不同热处理时间后(170℃),裂解表征产物的变化规律和产率差异。研究了PVC—RM的内耗(tanδ)与温度的关系,PVC—RM的玻璃化温度(Tg)为85℃。研究表明:PVC—RM不是PVC和RM(红泥)的简单共混物。在RM的作用下,PVC分子链支化碳原子上的活泼氯原子发生取代反应,形成C—O—Si键。因此,PVC—RM的高温裂解机理与PVC不同,且热稳定性较高。