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Synthesis and characterization of modular polyphosphonate homopolymers and copolymers
Author(s) -
Totsch Timothy R.,
Stanford Victoria L.,
Klep Oleksander,
Burdette Mary K.,
Grant Benjamin,
Foulger Stephen H.,
Gray Gary M.
Publication year - 2020
Publication title -
journal of polymer science
Language(s) - English
Resource type - Journals
eISSN - 2642-4169
pISSN - 2642-4150
DOI - 10.1002/pol.20200066
Subject(s) - copolymer , chalcogen , chemistry , diol , polymer chemistry , nuclear magnetic resonance spectroscopy , condensation polymer , polymer , organic chemistry
Abstract Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O] n – (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt 2 ) 2 and a diol (HOR′OH = 1,4‐cyclohexanedimethanol, 1,4‐benzenedimethanol, tetraethylene glycol, or 1,12‐dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt 2 ) 2 and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O] (x + 2) –[P(Ph)(X)OR′O] (x + 3) – (X = S or Se) have been synthesized by the polycondensations of Et 2 N[P(Ph)(X)OR′O] (x + 2) P(Ph)NEt 2 oligomers with HOR′O[P(Ph)(X)OR′O] (x + 3) H oligomers followed by reaction with a chalcogen. The Et 2 N[P(Ph)(X)OR′O] (x + 2) P(Ph)NEt 2 oligomers are prepared by the reaction of an excess of P(Ph)(NEt 2 ) 2 with a diol while the HOR′O[P(Ph)(X)OR′O] (x + 3) H oligomers are prepared by the reaction of P(Ph)(NEt 2 ) 2 with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using 1 H, 13 C{ 1 H}, and 31 P{ 1 H} NMR spectroscopy, TGA, DSC, and SEC. 31 P{ 1 H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and T g profiles. The polymers have weight average MWs of up to 3.8 × 10 4 Da.