【作者】 韩念凤；

【导师】 刘宗林；

【作者基本信息】 山东大学 ， 高分子化学与物理， 2006， 博士

【摘要】 聚硅基酯是一类主链中含有硅酯键的聚合物，由于硅酯键易受到亲核试剂的进攻，容易分解成小分子，因此聚硅基酯可以作为一种可降解高分子材料。亲核试剂进攻硅基酯时，可以进攻羰基碳和硅原子两个位置，这主要取决于硅原子上的取代基的立体效应和电子效应，取代基的位阻越大，给电子能力越大，则亲核试剂越易进攻羰基碳，反之，则易进攻硅原子。从而可以通过改变硅原子上的取代基以及主链的组成来改变聚硅基酯的降解速度。聚硅基酯的降解速度具有可调性和预见性并且其降解产物是无毒或者基本无毒的，所以聚硅基酯作为一种新型的可降解聚合物，有望用来做药物载体或可降解的涂料、粘附剂、染料等。 聚硅基酯的合成方法的探索和性质的研究引起人们的关注。Karen L. Wooley等人已经报道了几种合成聚硅基酯的方法，包括AA／BB型硅转移酯基交换法、AB型硅基转移酯基交换法、AB硅氢化反应以及AB和AB_n型交叉去氢偶联反应等方法。尽管如此，但是文献所报道的合成方法及合成的化合物还是有限的。本研究旨在寻找新的方法和合成新的化合物。经过一系列的实验及结果分析，我们发现了利用二元羧酸二叔丁基酯与氯硅烷缩聚合成聚硅基酯的新方法。利用该方法得到了一系列线型的、超支化的聚硅基酯，并对主链上含有不饱和双键的聚硅基酯进行交联反应研究。本论文主要内容分为以下四部分： 1、二元羧酸二叔丁基酯与氯硅烷缩聚法的探索更多还原

【Abstract】 Poly(silyl ester)s which have large numbers of silyl ester bonds in the polymer backbones could break down into small-molecule byproducts, so poly(silyl ester)s could been a new type of degradable material. Nucleophilic attack on acyloxysilane groups can occur at both the silicon atom and the carbonyl carbon. As substituents with increasing steric bulk or increasing electron-donating capabilities are attached to the silicon, an increasing amount of attack occurs at the carbonyl. Otherwise, an increasing amount of attack occurs at the silicon atom. So the degradation rate could vary by changing the substituents attached to the silicon atoms and the composition of the backbone. The degradable rate of the poly(silyl ester)s was variable and predictable degradation behavior and the degradation products from poly(silyl ester)s were innoxious or approximately innoxious, so the applications such as matrices for drug release, temporary coatings, temporary adhesives, or other purposes are envisioned.The study about the synthesis routes and the properties of poly(silyl ester)s have received considerable interest. Several routes have been reported by Karen L. Wooley to synthesize poly(silyl ester)s including transsilylation of AA/BB monomer systems, transsilylation of AB monomer systems, hydrosilylation of AB monomer systems and cross-dehydro coupling-based polymerizations of AB and AB_n monomer systems.更多还原