Synthesis and copolymerization of new phosphorus‐containing acrylates

Abstract

Two phosphorus-containing acrylate monomers were synthesized from the reaction of ethyl ␣-chloromethyl acrylate and t-butyl ␣-bromomethyl acrylate with triethyl phosphite. The selective hydrolysis of the ethyl ester monomer with trimethylsilyl bromide (TMSBr) gave a phosphonic acid monomer. The attempted bulk polymerizations of the monomers at 57-60°C with 2,2Ј-azobisisobutyronitrile (AIBN) were unsuccessful; however, the monomers were copolymerized with methyl methacrylate (MMA) in bulk at 60°C with AIBN. The resulting copolymers produced chars on burning, showing potential as flame-retardant materials. Additionally, ␣-(chloromethyl)acryloyl chloride (CMAC) was reacted with diethyl (hydroxymethyl)phosphonate to obtain a new monomer with identical ester and ether moieties. This monomer was hydrolyzed with TMSBr, homopolymerized, and copolymerized with MMA. The thermal stabilities of the copolymers increased with increasing amounts of the phosphonate monomer in the copolymers. A new route to highly reactive phosphorus-containing acrylate monomers was developed. A new derivative of CMAC with mixed ester and ether groups was synthesized by substitution, first with diethyl (hydroxymethyl)phosphonate and then with sodium acetate. This monomer showed the highest reactivity and gave a crosslinked polymer. The incorporation of an ester group increased the rate of polymerization. The relative reactivities of the synthesized monomers in photopolymerizations were determined and compared with those of the other phosphorouscontaining acrylate monomers. Changing the monomer structure allowed control of the polymerization reactivity so that new phosphorus-containing polymers with desirable properties could be obtained.

Recent Developments of New Components for Dental Adhesives and Composites

“…In this context, it should be mentioned that highly phosphonated double hydrophilic block copolymers based on poly(ethylene glycol) and poly(AEPA-1) blocks can control the morphology of calcium carbonate from smooth spherical structures to porous structures even at a rather low polymer concentration due to the strong effect of the phosphonate groups on the crystallisation of the mineral. [15] A number of acrylate phosphonic acids APA-1 to APA-3 ( Figure 4) were reported by Avcy et al [16,17] Unfortunately, the free-radical bulk polymerisation of phosphorus-containing acrylate monomer APA-1 was unsuccessful. [16] This was also observed with other vinyl phosphorus monomers.…”

“…[15] A number of acrylate phosphonic acids APA-1 to APA-3 ( Figure 4) were reported by Avcy et al [16,17] Unfortunately, the free-radical bulk polymerisation of phosphorus-containing acrylate monomer APA-1 was unsuccessful. [16] This was also observed with other vinyl phosphorus monomers. It was explained by steric effects in the propagation reaction [18] and was confirmed by quantum mechanical calculations in the case of APA-2.…”

Thermal degradation and combustion of a novel UV curable coating containing phosphorus

“…Phosphorus-containing monomers/oligomers used as flame retardants for UV curable systems have drawn much attention [8][9][10][11]. Their main advantages are low toxicity and the absence of dioxin and halogen acids, as well as the low evolution of smoke in the case of fire.…”

Phosphonic acid‐based amphiphilic diblock copolymers derived from ROMP

“…[15][16][17] Phosphorus-containing polymers have broad application areas; besides their flameretardant properties, 18 they are also used in biomaterials for their adhesive properties to metals, bone, and dentin. [19][20][21][22] The incorporation of phosphonic acid into acrylic monomers used in the dental industry can promote both biocompatibility and adhesion to the teeth, because of the formation of calcium phosphonates and phosphonate complexes. 21,[23][24][25] Phosphonates, corresponding anions of phosphonic acid, have strong interactions with and adsorb very powerfully onto mineral surfaces.…”