Effect of Different Acid Initiators on Branched Poly(propylenimine) Synthesis and CO2 Sorption Performance
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 »
- Authors:
-
- Georgia Inst. of Technology, Atlanta, GA (United States)
- Global Thermostat LLC, New York, NY (United States)
- Publication Date:
- 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.
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
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.
@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}
}
Web of Science