聚氯乙烯三乙撑四胺负载钯配合物的制备及对Heck反应的催化性能

以聚氯乙烯为原料, 通过胺化反应制得聚氯乙烯三乙撑四胺, 然后用较简单方法得到聚氯乙烯三乙撑四胺负载钯配合物(PVC-TETA-Pd), 利用XPS, TG, DTA和TEM等手段对其进行了表征. 热分析表明PVC-TETA-Pd在室温至250 ℃范围内有很好的热稳定性; TEM分析证实钯在PVC-TETA-Pd中分布比较均匀, 钯颗粒呈球形, 粒径在2～3 nm. PVC-TETA-Pd不需在惰性气体氛围中就能有效地催化丙烯酸、苯乙烯与芳基碘的Heck芳基化反应, 并且在较低的温度(40 ℃)或较少的催化剂用量(0.02%)下, 对Heck反应仍有较好的催化性能. PVC-TETA-Pd便于回收, 且有很好的重复使用性能, 对于碘苯与丙烯酸的反应, 重复使用十二次, 肉桂酸的产率仍达到80.1%.

Synthesis of Polyvinyl Chloride-triethylene-tetramine Supported Palladium Complex and Its Catalytic Properties for Heck Reaction

Polyvinyl chloride-triethylene-tetramine was synthesized from polyvinyl chloride via amination, then polyvinyl chloride-triethylene-tetramine supported palladium complex (PVC-TETA-Pd) was prepared and characterized by XPS, TG, DTA, TEM, etc. PVC-TETA-Pd has good thermal stability from room temperature to 250 ℃. TEM confirms that Pd particles are spherical and have uniform distribution with the size of 2～3 nm. The complex is an efficient catalyst for Heck arylation of acrylic acid and styrene with iodoarenes under atmospheric condition, even at the low temperature (40 ℃) or few amount of the catalyst (0.02 mol% Pd). PVC-TETA-Pd can be easily separated and used repeatedly. Yield of cinnamic acid was 80.1% for Heck reaction of acrylic acid with iodoarene even though the complex was used 12 times.