Morphological impact of segment dispersity in lithium salt-doped poly(styrene)/poly(ethylene oxide) triblock polymers

Hongyun Xu, Eric M. Greve, Mahesh Mahanthappa

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Abstract

We investigate the impact of center segment dispersity on the phase behavior of 17 lithium salt-doped poly(styrene-block-oligo(ethylene oxide) carbonate-block-styrene) (bSOS) triblock polymers, in which broad dispersity O blocks (Ä O = Mw/Mn ≈ 1.45) are situated between narrow dispersity S segments (Ä S ≤ 1.18) with volume fractions fO = 0.33-0.69 and total Mn = 11.6-43.8 kg/mol. Broad dispersity bSOS triblocks are synthesized by a tandem polycondensation and atom transfer radical polymerization reaction sequence. Using temperature-dependent small-Angle X-ray scattering, we map the morphology diagrams for bSOS samples variously doped with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) with r = (mol Li+)/(mol ethylene oxide) = 0.00-0.09. As compared to the phase behavior exhibited by 13 LiTFSI-doped, narrow dispersity SOS triblocks with fO = 0.30-0.58 and Mn = 7.1-45.2 kg/mol, we demonstrate that O segment dispersity shifts the lamellar morphology window to higher fO/salt and the lamellar microdomains dilate at each r value. The critical segregation strength for microphase separation is calculated to be (χN/2)ODT = 10.3-11.1 for r = 0.01-0.05 as compared to the mean-field theory prediction (χN/2)ODT = 8.95. These findings are interpreted in terms of a competition between amplified monomer concentration fluctuations due to O segment dispersity in these high χ/low N triblocks and ordered morphology stabilization due to preferential lithium salt solvation in the O domains. ©

Original languageEnglish (US)
Pages (from-to)5722-5734
Number of pages13
JournalMacromolecules
Volume52
Issue number15
DOIs
StatePublished - Aug 13 2019

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Styrene
Polyethylene oxides
Lithium
Polymers
Salts
Imides
Ethylene Oxide
Phase behavior
Ethylene
Microphase separation
Mean field theory
Oxides
Atom transfer radical polymerization
Carbonates
Solvation
Polycondensation
X ray scattering
Volume fraction
Stabilization
Monomers

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Morphological impact of segment dispersity in lithium salt-doped poly(styrene)/poly(ethylene oxide) triblock polymers. / Xu, Hongyun; Greve, Eric M.; Mahanthappa, Mahesh.

In: Macromolecules, Vol. 52, No. 15, 13.08.2019, p. 5722-5734.

Research output: Contribution to journalArticle

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N2 - We investigate the impact of center segment dispersity on the phase behavior of 17 lithium salt-doped poly(styrene-block-oligo(ethylene oxide) carbonate-block-styrene) (bSOS) triblock polymers, in which broad dispersity O blocks (Ä O = Mw/Mn ≈ 1.45) are situated between narrow dispersity S segments (Ä S ≤ 1.18) with volume fractions fO = 0.33-0.69 and total Mn = 11.6-43.8 kg/mol. Broad dispersity bSOS triblocks are synthesized by a tandem polycondensation and atom transfer radical polymerization reaction sequence. Using temperature-dependent small-Angle X-ray scattering, we map the morphology diagrams for bSOS samples variously doped with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) with r = (mol Li+)/(mol ethylene oxide) = 0.00-0.09. As compared to the phase behavior exhibited by 13 LiTFSI-doped, narrow dispersity SOS triblocks with fO = 0.30-0.58 and Mn = 7.1-45.2 kg/mol, we demonstrate that O segment dispersity shifts the lamellar morphology window to higher fO/salt and the lamellar microdomains dilate at each r value. The critical segregation strength for microphase separation is calculated to be (χN/2)ODT = 10.3-11.1 for r = 0.01-0.05 as compared to the mean-field theory prediction (χN/2)ODT = 8.95. These findings are interpreted in terms of a competition between amplified monomer concentration fluctuations due to O segment dispersity in these high χ/low N triblocks and ordered morphology stabilization due to preferential lithium salt solvation in the O domains. ©

AB - We investigate the impact of center segment dispersity on the phase behavior of 17 lithium salt-doped poly(styrene-block-oligo(ethylene oxide) carbonate-block-styrene) (bSOS) triblock polymers, in which broad dispersity O blocks (Ä O = Mw/Mn ≈ 1.45) are situated between narrow dispersity S segments (Ä S ≤ 1.18) with volume fractions fO = 0.33-0.69 and total Mn = 11.6-43.8 kg/mol. Broad dispersity bSOS triblocks are synthesized by a tandem polycondensation and atom transfer radical polymerization reaction sequence. Using temperature-dependent small-Angle X-ray scattering, we map the morphology diagrams for bSOS samples variously doped with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) with r = (mol Li+)/(mol ethylene oxide) = 0.00-0.09. As compared to the phase behavior exhibited by 13 LiTFSI-doped, narrow dispersity SOS triblocks with fO = 0.30-0.58 and Mn = 7.1-45.2 kg/mol, we demonstrate that O segment dispersity shifts the lamellar morphology window to higher fO/salt and the lamellar microdomains dilate at each r value. The critical segregation strength for microphase separation is calculated to be (χN/2)ODT = 10.3-11.1 for r = 0.01-0.05 as compared to the mean-field theory prediction (χN/2)ODT = 8.95. These findings are interpreted in terms of a competition between amplified monomer concentration fluctuations due to O segment dispersity in these high χ/low N triblocks and ordered morphology stabilization due to preferential lithium salt solvation in the O domains. ©

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