Polymerization of cyclic esters of phosphoric acid. VI. Poly(alkyl ethylene phosphates). Polymerization of 2‐alkoxy‐2‐oxo‐1,3,2‐dioxaphospholans and structure of polymers

Abstract

Abstract Five‐membered cyclic esters of phosphoric acid of the general formula: CH 2 CH(R)OP(O)‐(OR′)O polymerize readily to solid, soluble polymers of high molecular weight without any rearrangement known for various tri‐ and pentavalent organophosphorus monomers. 1 H‐, 13 C‐, and 31 P‐NMR spectra of polymers confirmed their linear structure: magnified image where R is H, with R′ = CH 3 , C 2 H 5 , n ‐C 3 H 7 , i ‐C 3 H 7 ; n ‐C 4 H 9 , CCl 3 CH 2 , or C 6 H 5 , or R is CH 2 Cl and R′ is C 2 H 5 . The use of n ‐C 4 H 9 Li, (C 5 H 5 ) 2 Mg, or ( i ‐C 4 H 9 ) 3 Al as initiators leads to polymers with M n = 10 4 –10 5 .