活性自由基聚合,在tempo.ppt

Evaluation only. Created with Aspose.Slides for .NET 3.5 Client Profile 5.2.0.0. Copyright 2004-2011 Aspose Pty Ltd.;Georges M K, et al. (Xerox Research Center of Canada) Macromolecules, 1993,36,2987-2988;2,2,4,4-四甲基派啶氮氧稳定自由基(2,2,4,4-tetramethyl-1-piperidinyloxy, TEMPO);分子量与转化率间线性关系！;1. NMP的发现及历史：;J. Am. Chem. SOC. 1994,116, 11185-11186;SOLOMON八十年代的工作：;SOLOMON八十年代的工作：;SOLOMON八十年代的工作：;1. NMP的发现及历史：;Rizzardo等与TEMPO/SFRP失之交臂？温度低，分布宽;双分子体系BPO:TEMPO=1:1.3;单分子体系(Unimolecular) ：;单分子体系可控效果优于双分子体系！;Typically these propagating carbon centered radicals are transient species , tend to disappear by self-termination, which is typically a diffusion controlled process. This raises the question, why do we only see minor amounts of irreversible termination in NMP? ;2. NMP的聚合机理;2. NMP的聚合机理;2. NMP的聚合机理;2.1 平衡的建立： persistent radical effect;2.1 平衡的建立： persistent radical effect;2.2 关于自由基的性质：;2.2 关于自由基的性质：;crossover experiments concluded nitroxides could freely diffuse. ;2.3 动力学与动力学参数;Negligible fraction of dead chains, ;;;2.3 动力学参数;2.3 动力学参数;N-tert-butyl-N-[1-diethylphosphono-(2,2-dimethylpropyl)] nitroxide (DEPN).;2.4 副反应;2.4 副反应;2.4 副反应;3. NMP聚合速率的提高;;3. NMP聚合速率的提高;Hawker等发现了一系列的酰化试剂,在TMPEP作为单分子引发剂时,123度下5个小时,苯乙烯的聚合可达到高的转化率,且分子量在15万以下可控,多分散性系数小于1.30。 Butz等发现在苯乙烯和丙烯酸丁酯的共聚中,添加醋酸酐(Ac2O)后聚合速率提高了近2倍.;4. NMP 的单体;;稳定性差！;;;;Evaluation only. Created with Aspose.Slides for .NET 3.5 Client Profile 5.2.0.0. Copyright 2004-2011 Aspose Pty Ltd.;非TEMPO:;;Evaluation only. Created with Aspose.Slides for .NET 3.5 Client Profile 5.2.0.0. Copyright 2004-2011 Aspose Pty Ltd.;;6. 嵌段共聚物的制备;嵌段顺序问题：先做酯，再做苯乙烯，成功！;嵌段共聚的可控性比均聚合好，分布窄！;One pot!;6. 星形、接枝等共聚物的制备;Evaluation only. Created with Aspose.Slides for .NET 3.5 Client Profile 5.2.0.0. Copyright 2004-2011 Aspose Pty Ltd.;Evaluation only. Created with Aspose.Slides for .NET 3.5 Client Profile 5.2.0.0. Copyright 2004-2011 Aspose Pty Ltd.;Evaluation only. Created with Aspose.Slides for .NET 3.5 Client Profile 5.2.0.0. Copyright 2004-2011 Aspose Pty Ltd.;Eval