AGET and SARA ATRP of styrene and methyl methacrylate mediated by pyridyl-imine based copper complexes

作者：Hsiao Chun Yu; Han Hui An; Lee Gene Hsiang; Peng Chi How^*

来源：European Polymer Journal, 2014, 51: 12-20.

DOI：10.1016/j.eurpolymj.2013.11.013

• AGET ATRP
• SARA ATRP
• Pyridyl-imine
• Cu(0)

Two pyridyl-imine ligands, N,N-dimethyl-N'-((pyridin-2-yl)methylene)-ethane-1,2-diamine (paenMe(2)) and N,N-diethyl-N'-((pyridin-2-yl)methylene)-ethane-1,2-diamine (PaenEt(2)), have been applied to AGET and SARA ATRP of styrene and methyl methacrylate. The polymeric products showed a narrow molecular weight distribution (M-w/M-n = 1.16-1.28) and a molecular weight that not only increased linearly with monomer conversion (>70%) but also matched to the theoretical value. The performance of Cu-II(paenMe(2))Br-2 and Cu-II(paenEt(2))Br-2 in AGET ATRP was almost the same and thus the steric effect between these two complexes was not significant. The activation rate constant (k(act)) of Cu-I(paen-Me-2)Br with PEBr was measured as 7.96 x 10(-3) M-1 s(-1) and the deactivation rate constant (k(deact)) was estimated as 2.8 x 10(5) M-1 s(-1). This kinetic measurement indicated that the improved control efficiency of pyridyl-imine based catalysts in AGET and SARA ATRP should be attributed to the high deactivator/activator (Cu-II species/Cu-I species) ratio that relatively enhanced the deactivation rate and lowered the radical concentration to minimize the influence of radical termination and other side reactions.

• 出版日期2014-2
• 单位清华大学