Phosphorus-Containing Allyl Monomers

Kahraman et described the synthesis of aromatic phosphorus-containing allyl monomers such as allyldiphenylphosphine oxide (ADPPO) or bis[4-(allylo3gr)phenyl] phenylphosphine oxide (DAPPO) (Scheme 3.14). The... 

Mizutani and Hirashima obtained by conventional radical polymerization a photosensitive resin using methacrylic acid, butyl acrylate, and a new phosphorus-containing allyl monomer (Scheme 3.20). To create the new monomer, they treated 9,10-dihydro-9-oxa-10-phosphaphenanthrene (DOPO) with allyl methacrylate at high temperature. By copolymerization with butyl acrylate, they obtained a photosensitive resin that showed good fire resistance. 

Only a few articles deal with the polymerization of phosphorus-containing allyl ether monomers. Most of them discuss radical polymerization however, the strong stability of allyl ether radicals is probably a disadvantage, leading to longer polymerization times compared with those of the more reactive vinyl ethers. 

Phosphorus-Based Polymers From Synthesis to Applications aims at providing a broad overview of recent developments in the synthesis and applications of phosphorus-containing polymers. Over the last few years, more and more research papers have been published on this field. Polymerization of different kinds of phosphorus-based monomers using various methods has been carried out (meth)acrylates, (meth)acrylamides, vinylphosphonic acid, styrenic, and allylic monomers. The resulting phosphorus-based materials have found applications in different domains biomedical, complexation with metals, fire retardant additives, fuel cell membranes, etc. 

The invention of Heath et al. relates to novel phosphonate allyl monomers, made from reaction of an unsaturated oxirane with amine- or hy-drojyl-functionalized phosphonic acids (Scheme 3.21). These monomers were copolymerized with other unsaturated species (acrylic acid, maleic acid, acrylamide, or monomer derivatives of sulfonic acid, etc), yielding phosphonate polymers or oligomers. Phosphorus-containing monomers were incorporated at a ratio of 0.1-30% and polymerized in aqueous media. The final polymers had a molecular weight of 800-30 000 g mol . With their phosphonic acids groups (free acid or salts forms), they are of particular use as oilfield scale inhibitors. 

Phosphonate monomers of type 1 were made from the reaction of allyl glycidyl ether with hydroxy-functionalized phosphonic acid. To obtain azo-phosphonated products (type 2), multicomponent reactions (amine-, aldehyde/ketone-, or phosphorus-containing compounds) such as the Kabachnick-Fields," Mannich," or Moedritzer ° reactions, were used. These reactions generated in a selective way the a-aminoallq lphosphonate products. 

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