Oxidative polymerizations of 2-(N

N-diethylamino)ethyl methacrylate (DEAEMA) as an intrinsically reducing inimer catalyzed by high-oxidation state transition metals (CuX2/ligand

FeX3/ligand

X=Cl or Br

ligand=2

2'-bipyridine

tetramethylethylenediamine

pentamethyldiethylenetriamine

CuSO4) were systematically investigated using gas chromatography

gel-peameation chromatography and multi-angle laser light scattering (MALLS) to monitor the monomer conversion

molecular weight (MW) and its distribution (MWD) of the PDEAEMA

respectively.The results showed that the high-oxidation state transition metals can steadily catalyze the free radical polymerization of DEAEMA with the reaction temperature ranging from 30℃ to 60℃ even in the absence of any chemical initiators

the MW of the PDEAMEA increased gradually with the conversion

while it maintained a rather broad MWD even from low conversions.The MALLS results showed that the absolute MW of the PDEAEMA showed an unusual multi-modal distribution.By comparing the CuSO4-catalyzed redox-initiation ability of lower-MW tertiary amines

it can be concluced that DEAEMA functions as an intrinsically reducing inimer under the catalysis of high-oxidation state transition metals

which oxidize the alpha CH (C-H) of the amine group of DEAEMA into the C radicals

initiating the conventional radical polymerization of DEAEMA and giving rise to linear PDEAEMA primary chains.Subsequently

the linear PDEAEMA chains serve as macro-initiators with high-oxidation state transition metals and initiate the graft polymerization of DEAEMA

leading to branched PDEAEMA with a certain number of side chains.It was inferred that self-initiated free radical polymerization of intrinsically reducing inimers under catalysis of high-oxidation state transition metals can produce long-chain-branched polymer via such a one-pot approach.