Synthesis of Phosphor Containing Monomer and Their ATRP

Phosphorus-containing polymers are involved in a large range of applications. For example, they have been used as adhesion promoters for paints, lacquers, and adhesives, flame-retardant additives, complexing agents to recover metal ions from the environment and industrial liquids, and agents for controlling crystallization of CaCO3 and also have been proposed for use in tissue engineering and drug controlled release because of their biocompatibility and biodegradability. Phosphorous-containing polymers have been prepared through various approaches. One of the methods of incorporating phosphorus functionality into polymers is the polymerization or copolymerization of phosphorus containing vinyl monomers such as vinyl and allyl phosphonates [1]. Polymers with phosphorus in the backbone are usually synthesized by either polycondensation or ring-opening methods [2]. Atom transfer radical polymerization (ATRP) [3], one of the most robust controlled/living radical polymerization (CRP) techniques which allows for the controlled polymerization of various monomers. Experimental Monomer 1 (DMMP) Synthesis. In this study, phosphonate monomer was synthesized and polymerized via ATRP. In the first step, diethyl (methacryloyloxy)methyl phosphonate (DMMP), was synthesized with methacryloyl chloride and triethylamine at -5 oC and under nitrogen (Figure 1). In the second step, diethyl (methacryloyloxy) methyl phosphonate was polymerized with CuBr/PMDETA catalytic system by using toluene as solvent at 70 oC. Figure 1. Reaction of diethyl(hydroxymethyl) phosphonate with methacryloyl chloride Monomer 2(PGMA) Synthesis. Diethylhydroxy methyl phosphonate and GMA were added to a round-bottom flask with a nitrogen inlet. The mixture was stirred at 50 oC for 5 h. (Figure 2). Figure 2. Phosphorylation of GMA Result and Discussion We were reported the synthesis of novel phosphonate polymers with a narrow molecular weight via DMMP monomer. This polymer was characterized by using gel permeation chromatography (GPC) and proton nuclear ...