【作者】 陈帅帅；

【导师】 罗时忠； 唐勇；

【作者基本信息】 安徽师范大学 ， 高分子化学与物理， 2011， 硕士

【摘要】 在聚乙烯材料的高分子链骨架中引入极性官能团对于提升聚乙烯材料的性能,拓展其应用范围具有重要的作用,特别是以其高分子链上极性基团为反应位点可以进一步合成接枝及嵌段共聚物。本论文对含聚乙烯链段多相聚合物的合成及应用进行了研究。论文第一部分研究了含聚乙烯链段接枝及嵌段共聚物的合成及应用。含配位边臂的β-酮亚胺钛金属配合物能高活性(> 10~6 g/mol·h·atm)地催化乙烯与异丁基铝保护的9-癸烯-1-醇的共聚反应。将插入率不同的共聚物转化成大分子引发剂,通过原子转移自由基聚合合成不同接枝率的主链为聚乙烯的接枝共聚物。同时我们利用新型的SHOP催化剂催化乙烯聚合,所得产物端烯聚乙烯经适当化学反应转化成大分子引发剂,通过原子转移自由基聚合合成不同链段长度和比率的嵌段共聚物。所合成的接枝及嵌段共聚物均可以作为良好的相容剂。论文的第二部分研究了乙烯与4-(10-十一烯)-吡啶的共聚,将吡啶基团负载到聚乙烯上。通过重氮转移生成吡啶叶立德的方式,我们实现了负载吡啶催化的叶立德形式[4+1]环化反应。在1 mol %的Fe(Tcpp)Cl的作用下,5 mol %的吡啶可以催化重氮乙酸乙酯和α-ylidene-β-diketones反应,以单一的非对映选择性、良好到优秀的产率得到二氢呋喃衍生物,并实现了催化剂的回收利用,而且其催化活性可至少保持至第3轮。更多还原

【Abstract】 The introduction of polar functional groups into polyethylene improves properties of material for wide applications. This thesis mainly focuses on the synthesis and application of multi-phase polymers containing polyethylene chains.In the first part, （O-NS）TiCl₃ complex which exhibits high catalytic activities （> 10⁶ g/mol·h·atm） has been used for the copolymerization of ethylene and 9-decen-1-ol. The copolymers that have different incorporations were converted to macromolecular initiators, graft copolymers were synthesized by atom transfer radical polymerization （ATRP）. Moreover, unsaturated polyethylene was prepared by novel Shell Higher Olefins Process （SHOP） catalyst, which was converted to macromolecular initiators, block copolymers were synthesized by ATRP. The copolymers can serve as a good compatibilizer of different materials.In the second part, 4-（undec-10-enyl）pyridine was triumphantly inserted into the polyethylene chains. This PE-supported pyridine proved to be an excellent recoverable and reusable organocatalyst. In the presence of catalytic amount of PE-supported pyridine and 1 mol % of Fe（Tcpp）Cl,α-ylidene-β-diketones reacted with diazoacetate affording dihydrofurans respectively in good yield with high diastereoselectivities. The catalyst could be easily recovered and used for three times at least.更多还原