【作者】 谭哲；

【导师】 暴峰；

【作者基本信息】 华中师范大学 ， 有机化学， 2009， 硕士

【摘要】 自从Maty]iasezwksi和王锦山首次报道了二联吡啶/Cu体系的原子转移催化聚合之后,关于原子转移自由基聚合(ATRP)的配体的研究一直在进行着,ATRP在获得低分子量分布的聚合产物方面有着其重要的意义,特别是在设计星形聚合物方面有着独特的优势,而且易于操作,选择适当的催化剂配体,可以提高ATRP的活性,并得到分子量分布好的聚合产物,这样的产物在材料的设计方面是有着很重要的作用。寻找合适的高活性催化剂配体,对于ATRP在工业上应用有着很大的价值。但是目前在催化剂配体的研究当中,合成出的配体具有较大的分子结构,其与金属配位之后的配体在溶剂中存在溶解度低,催化活性较低的缺点。因此,寻找适当的的催化剂使其配合物在溶剂中有较好的溶解度,提高其催化活性是目前研究ATRP的重要工作。本文以本实验室合成的双-1-苯基-1,3-二酮基苯在无水无氧条件下催化甲基丙烯酸甲酯、苯乙烯能得到分子量分布比较窄的聚合产物的实验为基础,设计并合成了最为简单的1,3-二酮化合物:1,1,2,2-四乙酰基乙烷,并用于反向原子转移催化聚合(RATRP)。由于1,1,2,2-四乙酰基乙烷的结构简单,在各种不同的非质子性溶剂中都有较好的溶解性,且其配合物在一定温度下在这些溶剂中也有较好的溶解度,在一定的条件下其催化甲基丙烯酸甲酯等单体具有较好的催化活性。实验结果表明,在一定条件下,以1,1,2,2-四乙酰基乙烷/Co和1,1,2,2-四乙酰基乙烷/Ni的催化体系对MMA具有很好的可控性。更多还原

【Abstract】 Since Matyjasezwksi and Wang JinShan first reported 4,4’-bipyridine/Cu in atom transfer radical polymerization(ATRP),the ligand of ATRP has been engaged in the researches.ATRP has important significance to obtain low-molecular-weight distribution in the polymer product,especially in the design of star-shaped polymers.Meanwhile,ATRP is easy to operation,and high activity catalyst can improve the atom transfer radical polymerization activity and get good molecular distribution polymerization products.So searching for suitable ligands highly active catalyst for atom transfer radical polymerization in the industrial application is of great value.However,in the study of ligand catalyst,most ligands synthesised usually have a larger molecular structure or low solubility in the solvent after they coordination with the metal which will influence the activity of the catalyst.Therefore,to find a appropriate solube catalyst in the solvent and enhance its catalytic activity is an important work study in atom transfer catalyzed polymerization.In this paper,basing on the laboratory work:bi-1-phenyl-1,3-diketone-benzene, which can get a rather narrow molecular weight distribution of polymer products in polymerization of methyl methacrylate and styene,we design and synthesis of the most simple compound:1,1,2,2-tetraacetyl ethane and work for the reverse atom transfer catalyzed polymerization.Because 1,1,2,2-tetraacetyl ethane has a simple structure and good solubility in a variety of non-proton solvents.Their complexes also have good solubility.Experiments show that under certain conditions in the catalytic methyl methacrylate monomer,such as a good catalytic activity.The experimental results show that under certain conditions,1,1,2,2-tetraacetyl ethane/Co and 1,1,2,2-tetraacetyl ethane/Ni systems have a very good controllable in polymerization of MMA.更多还原