Effect of Different Acid Initiators on Branched Poly(propylenimine) Synthesis and CO2 Sorption Performance

Sarazen, Michele L.; Sakwa-Novak, Miles A.; Ping, Eric W.; Jones, Christopher W.

doi:10.1021/acssuschemeng.9b00512

Title: Effect of Different Acid Initiators on Branched Poly(propylenimine) Synthesis and CO₂ Sorption Performance

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Abstract

Branched poly(propylenimine) (PPI) provides an alternative to the prototypical amine polymer, commercially available branched poly(ethylenimine) (PEI), in composite adsorbents for CO₂ capture. Herein, we investigate the synthesis of PPI via cationic ring opening polymerization of azetidine using various acid initiators (HBr, HClO₄, HCl, CH₃SO₃H) and polymerization times, impacting the molecular weight and CO₂ sorption behavior. The polymerization kinetics and the amine distribution (i.e., primary:secondary:tertiary ratios) are monitored with ¹H NMR during polymerization, and a basic ion-exchange resin is used to neutralize charged amine centers and to remove unreacted acid. The polymers are impregnated into the model porous oxide support, mesoporous silica SBA-15, and the CO₂ capacities under both simulated ambient air and flue gas conditions are elucidated. In parallel, the oxidative stability of the PPI-based sorbents is assessed and compared with the prototypical PEI sorbents. Sorbents with 30 wt % polymers synthesized using HBr and HClO₄ exhibit higher CO₂ capacities than those made with HCl or CH₃SO₃H. Sorbents from HBr polymers only lost 24% of their CO₂ capacity after 12 h of oxidation in air at 383 K. Even trace amounts of residual ClO₄^– anions in HClO₄ initiated polymers, though, accelerated oxidation (decreased CO₂ capacity by 64%). In conclusion, extendedmore »« less

Authors:

Sarazen, Michele L. ^[1]; Sakwa-Novak, Miles A. ^[2]; Ping, Eric W. ^[2];

^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)
Global Thermostat LLC, New York, NY (United States)

Publication Date:: Mon Mar 11 00:00:00 EDT 2019

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME); Georgia Institute of Technology, Atlanta, GA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1566588

Grant/Contract Number:: SC0012577

Resource Type:: Accepted Manuscript

Journal Name:: ACS Sustainable Chemistry & Engineering

Additional Journal Information:: Journal Volume: 7; Journal Issue: 7; Journal ID: ISSN 2168-0485

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); defects; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats


                    Sarazen, Michele L., Sakwa-Novak, Miles A., Ping, Eric W., and Jones, Christopher W. Effect of Different Acid Initiators on Branched Poly(propylenimine) Synthesis and CO2 Sorption Performance.  United States: N. p., 2019. 
Web.  doi:10.1021/acssuschemeng.9b00512.

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                    Sarazen, Michele L., Sakwa-Novak, Miles A., Ping, Eric W., & Jones, Christopher W. Effect of Different Acid Initiators on Branched Poly(propylenimine) Synthesis and CO2 Sorption Performance.  United States.  https://doi.org/10.1021/acssuschemeng.9b00512

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                    Sarazen, Michele L., Sakwa-Novak, Miles A., Ping, Eric W., and Jones, Christopher W. Mon .  
"Effect of Different Acid Initiators on Branched Poly(propylenimine) Synthesis and CO2 Sorption Performance".  United States.  https://doi.org/10.1021/acssuschemeng.9b00512.  https://www.osti.gov/servlets/purl/1566588.

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@article{osti_1566588,

  title        = {Effect of Different Acid Initiators on Branched Poly(propylenimine) Synthesis and CO2 Sorption Performance},

  author       = {Sarazen, Michele L. and Sakwa-Novak, Miles A. and Ping, Eric W. and Jones, Christopher W.},

  abstractNote = {Branched poly(propylenimine) (PPI) provides an alternative to the prototypical amine polymer, commercially available branched poly(ethylenimine) (PEI), in composite adsorbents for CO2 capture. Herein, we investigate the synthesis of PPI via cationic ring opening polymerization of azetidine using various acid initiators (HBr, HClO4, HCl, CH3SO3H) and polymerization times, impacting the molecular weight and CO2 sorption behavior. The polymerization kinetics and the amine distribution (i.e., primary:secondary:tertiary ratios) are monitored with 1H NMR during polymerization, and a basic ion-exchange resin is used to neutralize charged amine centers and to remove unreacted acid. The polymers are impregnated into the model porous oxide support, mesoporous silica SBA-15, and the CO2 capacities under both simulated ambient air and flue gas conditions are elucidated. In parallel, the oxidative stability of the PPI-based sorbents is assessed and compared with the prototypical PEI sorbents. Sorbents with 30 wt % polymers synthesized using HBr and HClO4 exhibit higher CO2 capacities than those made with HCl or CH3SO3H. Sorbents from HBr polymers only lost 24% of their CO2 capacity after 12 h of oxidation in air at 383 K. Even trace amounts of residual ClO4– anions in HClO4 initiated polymers, though, accelerated oxidation (decreased CO2 capacity by 64%). In conclusion, extended resin treatments were needed to leave undetectable Cl content in these polymers, which resulted in sorbents that are much more oxidatively stable.},

  doi          = {10.1021/acssuschemeng.9b00512},

  journal      = {ACS Sustainable Chemistry & Engineering},

  number       = 7,

  volume       = 7,

  place        = {United States},

  year         = {Mon Mar 11 00:00:00 EDT 2019},

  month        = {Mon Mar 11 00:00:00 EDT 2019}

}

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Title: Effect of Different Acid Initiators on Branched Poly(propylenimine) Synthesis and CO2 Sorption Performance

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Title: Effect of Different Acid Initiators on Branched Poly(propylenimine) Synthesis and CO₂ Sorption Performance