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氨基酸衍生物铜(Ⅱ)、镍(Ⅱ)配合物催化剂的合成与表征及催化甲基丙烯酸甲酯聚合研究

Syntheses and Characterizations of Copper(Ⅱ)、Nickel(Ⅱ) Complexes Containing Amino Acid Derivative Ligands and Studys on Their Catalysis for MMA Polymerization

【作者】 王晓琴

【导师】 翁家宝;

【作者基本信息】 福建师范大学 , 物理化学, 2010, 硕士

【摘要】 本文合成并表征了如图所示的氨基酸席夫碱铜(Ⅱ)配合物(1),氨基酸席夫碱镍(Ⅱ)配合物(2),新型氨基酸衍生物配体(N,N’-均苯四酸-2-L-氨基酸二酸)(3),并通过元素分析,红外光谱以及核磁共振进行结构表征。本文采用反向原子转移自由基聚合(RATRP)的方法,以自己设计合成的配合物氨基酸席夫碱铜(Ⅱ)配合物、氨基酸席夫碱镍(Ⅱ)配合物或氨基酸衍生物配体与铜的络合物为催化剂,二甲苯或乙腈为溶剂,2-溴异丁酸乙酯(EBIB)作为引发剂,进行甲基丙烯酸甲酯(MMA)的活性聚合。通过傅立叶红外(FTIR),氢谱核磁共振(1H-NMR),碳谱核磁共振(13C-NMR)和凝胶色谱仪(GPC)研究聚甲基丙烯酸甲酯(PMMA)的结构以及性质。采用氨基酸席夫碱铜(Ⅱ)、镍(Ⅱ)配合物以及氨基酸衍生物/氯化铜三种催化体系,对甲基丙烯酸甲酯的均聚反应进行研究。研究发现以上三种催化体系均可以有效的催化MMA的聚合。详细分析了反应温度、反应时间对氨基酸席夫碱金属配合物催化体系催化MMA聚合行为的影响,结果表明氨基酸席夫碱金属配合物催化体系的最佳聚合温度为80℃。在80℃条件下,聚合反应的转化率随时间的延长而增加,到12h时氨基酸席夫碱铜(Ⅱ)配合物催化体系转化率达到最大值接近于100%。这说明温度为80℃,时间12h是氨基酸席夫碱铜(Ⅱ)配合物催化体系催化MMA聚合的最佳条件。

【Abstract】 In this paper, copper(Ⅱ) complexes containing amino acids Schiff bases ligands(1), nickel(Ⅱ) complexes containing amino acids Schiff bases ligands(2), a new amino acid derivatives ligands(3)(as seen in the following figure) were synthesized and characterized by EA, FTIR and 1H-NMR.Reverse atom transfer radical polymerization(RATRP) of methyl methacrylate (MMA) have been carried out under the condition using EBIN initiator with copper(Ⅱ) complexes containing amino acids Schiff bases ligands, nickel(Ⅱ) complexes containing amino acids Schiff bases ligands, copper(Ⅱ) complexes containing amino acid derivatives ligands as the catalyst and xylene or acetonitrile as solvent. The structure and properties of products(PMMA) were characterized by FTIR,1H-NMR,13C-NMR and GPC.The vinyl-polymerizations of MMA have been studied in detail by using copper(Ⅱ) complexes containing amino acids Schiff bases ligands, nickel(Ⅱ) complexes containing amino acids Schiff bases ligands, copper(Ⅱ) complexes containing amino acid derivatives ligands catalytic systems. All above catalytic systems were found to be efficient for the polymerization of MMA. We also studied the influence of reaction temperature, reaction time for polymerization of MMA. The experimental results show that the optimum polymerization temperature of MMA using complexes containing amino acids Schiff bases ligands as catalyst was 80℃. At this temperature, extending reaction time can help to increase conversion, and the conversion of copper(Ⅱ) complexes catalytic systems was up to the higest value at 12 hours. It explains the copper(Ⅱ) complexes containing amino acids Schiff bases ligands catalytic systems are excellent for polymerization of MMA at 80℃,12 hours.

  • 【分类号】O643.36;O631.5
  • 【被引频次】1
  • 【下载频次】137
  • 攻读期成果
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