Synthesis and characterization of carbamoylphosphonate monomer and its copolymer with styrene. II

Abstract

A monomer, diethyl α,α‐dimethyl‐m‐isopropenylbenzyl carbamoylphosphonate, has been prepared by the base‐catalyzed reaction of the isocyanate m‐TMI (α,α‐dimethyl‐m‐isopropenylbenzylisocyanate) with diethyl phosphite. The structure of the carbamoylphosphonate monomer and its styrene copolymer was confirmed spectroscopically, and the nature of the hydrogen bondings in the NHC(O)P(O)(OR)2 unit in the monomer and copolymer is discussed in detail. A bulk polymerization of the carbamoylphosphonate is very slow and tends to yield a crosslinked product, but a solution polymerization produced the soluble copolymers. The Tg(midpoint) of the homo‐polymer is low, 67°C, and its capacity to complex UO2(NO3)2 is very high, 28 wt % (19 mol %). © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 889–899, 1997

Synthesis and Mechanism of PBI Phosphonate, Poly[2,2′-(-m-phenylene)-5,5′-Bibenzimidazole Phosphonate Ester], and its Polyphosphonic Acid Derivatives

“…Functionalization of macromolecules with phosphonate ester groups has been shown to impart many desirable properties such as solubility in a wide variety of organic solvents, − miscibility with other polymers, , metal coordinating ability − ,− and adhesive properties. − Most of the unique properties are due to the −C−PO group which is a proton acceptor and thus enables the macromolecule to form a hydrogen bond and interact with Lewis acids. Additionally, the polyphosphonate esters may be hydrolyzed to the corresponding polyphosphonic acids.…”

“…Scheme 2) 1. H NMR (600 MHz in DMSO-d 6 ), δ (ppm): 1.20 (t, 6H, CH 3 CH 2 O), 2.03 (s, 3H, CH 3 CdO), 3.00 (s, 3H, N(CH 3 )CH 2 ), 4.09 (m, 3.8H, CH 3 CH 2 O), 5.80 (s, 2H, N-(CH 3 )CH 2 ), 7.35 (td, 1H, H 6 ), 7.64 (dd, 1H, H 5 ), 7.95 (d, 1H, H 7 ), 8.48 (s, 1H, -N-CHdN-).…”

ChemInform Abstract: Facile “One‐Pot” Preparation of Phosphonothiolformates. Useful Reagents for the Synthesis of Carbamoylphosphonates.

“…Phosphonic acids with heteroatoms in the a and/or b positions have attracted much attention recently for their involvement in biologically relevant processes such as inhibition of renin 1 and HIV protease 2,3 and for their use as haptens in the development of catalytic antibodies. 4 Particularly, carbamoylphosphonates have been reported as having antiviral, 5 and herbicidal activity, 6 as well as applied to the synthesis of new class of polymers 7 and bidentate organophosphorus ligands. 8 Reetz et al reported the synthesis of carbamoylphosphonates by reaction of dialkyl phosphite and isocyanates.…”