Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt2)2and 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)(NEt2)2and 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 Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2oligomers with HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers followed by reaction with a chalcogen. The Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2oligomers are prepared by the reaction of an excess of P(Ph)(NEt2)2with a diol while the HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers are prepared by the reaction of P(Ph)(NEt2)2with 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 using1H,13C{1H}, and31P{1H} NMR spectroscopy, TGA, DSC, and SEC.31P{1H} 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
Polyphosphonates, a class of polymers with the generic formula –[P(R)(X)–OR'O]n–, exhibit a high degree of modularity due to the range of R, R', and X groups that can be incorporated. As such, these polymers may be designed with a polyethylene oxide (PEO) backbone (R' group) and employed as solid polymer electrolytes (SPEs). Two PEO‐containing polyphosphonate analogs (R = Ph; X = S or Se) were doped with LiPF6and their conductivities were measured. Conductivities were similar (X = S) to or exceeding (X = Se) those of standard PEO systems (just below 10−4S/cm at 100°C). Binding models for Li+were generated using31P{1H}NMR titration experiments. Binding of Li+by these polyphosphonates followed a positive cooperativity model, and varying the X group (S or Se) affected the observed cooperativity (Hill coefficient = 1.73 and 4.16, respectively). The presence of Se also leads to an increase in conductivity as temperature is raised above the Tg, which is likely an effect of reduced Columbic interactions. Because of their modularity and ease with which cation binding can be evaluated using31P{1H} NMR titration experiments, polyphosphonates offer a unique approach for the modification of Li+ion battery technology.
more » « less- Award ID(s):
- 1632881
- NSF-PAR ID:
- 10240590
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Polymer Science
- Volume:
- 59
- Issue:
- 2
- ISSN:
- 2642-4150
- Page Range / eLocation ID:
- p. 139-145
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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