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              <p>The present study deals with the MADIX polymerizations of dimethyl vinyl phosphonate (DMVP) and vinyl phosphonic acid (VPA). The high transfer activity of O-ethyl xanthates during the MADIX polymerization of vinyl phosphonates is demonstrated. MALDI-TOF MS analysis shed light on intrinsic limitations for DMVP polymerization due to significant hydrogen transfer reactions, thereby limiting MADIX control to oligomerization. More importantly, the efficiency of xanthates in homopolymerizing VPA according to a MADIX mechanism constitutes a great potential for the direct engineering of phosphonic acid-containing complex polymer architectures.</p>
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