Synthesis and polymerization of phosphorus‐containing acrylates

Abstract

Novel phosphorus-containing acrylate monomers were synthesized by two different routes. The first involved the reaction of ethyl ␣-chloromethyl acrylate and t-butyl ␣-bromomethyl acrylate with diethylphosphonoacetic acid. The monomers were bulk-and solution-polymerized at 56 -64°C with 2,2Ј-azobisisobutyronitrile. The ethyl ester monomer showed a high crosslinking tendency under these conditions. The selective hydrolysis of the ethyl ester phosphonic ester compound was carried out with trimethylsilyl bromide, producing a phosphonic acid monomer. In the second route, ethyl ␣-hydroxymethyl acrylate and t-butyl ␣-hydroxymethyl acrylate were reacted with diethylchlorophosphate. The bulk homopolymerization and copolymerization of these monomers with methyl methacrylate and 2,2Ј-azobisisobutyronitrile gave soluble polymers. The attempted hydrolysis of the monomers was unsuccessful because of the loss of the diethylphosphate group. The relative reactivities of the monomers in the photopolymerizations were also compared. The ethyl ␣-hydroxymethyl acrylate/diethylphosphonic acid monomer showed higher reactivity than the other monomers, which may explain the crosslinking during the polymerization of this monomer. The reactivities of other derivatives were similar, but the rates of polymerization were slow in comparison with those of methyl methacrylate.

Polyglycidol-based metal adhesion promoters

“…[4][5][6][7] Most commonly however, low molecular weight molecules carrying phosphonic acids are studied, as these form well-dened selfassembled monolayers. [14][15][16][17][18][19][20] Poly(phosphonate)s and phosphonated (meth-)acrylates are biocompatible, which permits their in vivo application for medical purposes. These phosphonates are hydrolytically more stable compared to the corresponding phosphates, since they possess a phosphorus-carbon bond.…”

Synthesis of dialkyl 2-(Methacryloyloxyethyl) phosphonates, their characterization and polymerization

“…These additives leach out when polymer containing such materials are subjected to different mechanical processing conditions or by ageing. This leads to decrease in their flame retarding effect [11][12][13][14][15].…”

“…The reactive approach for the enhancement of fire resistance involves, design of new, intrinsically flame retarding polymer or by chemical modification of existing polymer by flame retardant moieties through co polymerization [11,[13][14][15]. The new group would be either part of a polymer main chain or as a pendant group.…”

“…This can be attributed to the ability of phosphorus to exist in variable oxidation states [10]. Phosphorus based polymers has found wide applications as dispersants [16], anticorrosion agents [16,17], lubricants [18], proton conducting fuel cell membranes for alternate energy production, adhesion promoters for paints and lacquers [15][16][17][18][19], as ion exchange resins [17,18,20], chelating agents for heavy metal salts [20], oxygen plasma resistance, poly mer supported catalysis, radiation resistance, selective metal binders [15] and in biomedical field as dental adhesives, as regenerative medicine, in tissue engi neering, as carriers for bioactive molecules, in devel oping biomimetic compounds, in drug delivery system etc. [16,18].…”

Synthesis of New Phosphorus-Containing (Co)Polyesters Using Solid-Liquid Phase Transfer Catalysis and Product Characterization

“…Among the main ways of obtaining phosphorus-containing polymers, especially polyphosphonates and polyphosphates, respectively, polyaddition reactions [10,11], polymerization [12], ring opening polymerization [13], polytransesterification [14], and polycondensation [15,16,17,18], phase transfer catalysis (PTC) or interfacial polycondensation reactions [19,20,21] have seen increasing development in the last years.…”