American Chemical Society
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Synthesis of Polyphosphorinanes. 1. Homopolymerization and Telomerization of Allyl Ether Phosphite

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journal contribution
posted on 2009-04-14, 00:00 authored by Claire Negrell-Guirao, Bernard Boutevin
Cyclic allyl phosphonated monomers were synthesized by transesterification reaction between a glycol bearing a double bond and a hydrogenophosphonate and were fully characterized by NMR and IR spectroscopy. Radical homopolymerization of these monomers was carried out at 70 °C in the presence of α,α′-azoisobutyronitrile (AIBN) as initiator and acetonitrile as solvent. The thus-obtained polymers showed two SEC distributions, one composed of oligomers (with Mn ≈ 800 g/mol) and one composed of high-molecular-weight polymers (with Mn ≈ 100 000 g/mol). The latter were hyperbranched polymers suffering from solubility limitations for future industrial applications. Therefore, telomerization of one phosphonated monomer using dimethyl hydrogenophosphonate (HP(O)(OMe)2) as a chain transfer agent (CTA) limited the hyperbranching through two concomitant mechanisms of polymerization, which are discussed. For R0 = 2 (R0 represents initial [CTA]0/[monomer]0 molar ratio), the results showed a limited chain length, whereas monoadduct formation occurred for a R0 value of 10.