Insights into Azetidine Polymerization for the Preparation of Poly(propylenimine)-Based CO2 Adsorbents
Abstract
The cationic ring-opening polymerization of azetidine to form branched poly(propylenimine) (PPI) is investigated for the purpose of evaluating the utility of PPI/silica composite adsorbents for CO2 capture. The polymerization kinetics and primary:secondary:tertiary amine distribution are monitored with 1H NMR during reaction with varied synthesis conditions (i.e., reaction time 20–150 h), temperature (343–353 K), and monomer to acid initiator (here, HClO4) ratio. It is found that primary amines are converted to tertiary amines with increased polymerization time, while the addition of monomer over the first 6 h of polymerization increases the primary amine content. This suggests a mechanism where the monomer is rapidly consumed, leaving dimers or small oligomers that still contain rings as key reaction centers. The synthesized polymer is neutralized with either NH4OH or a basic resin and impregnated into mesoporous silica (SBA-15). The CO2 capture properties of these composite adsorbents are investigated, giving information about the effectiveness of the acid neutralization processes.
- Authors:
-
[1]
- Georgia Inst. of Technology, Atlanta, GA (United States). School of Chemical and Biomolecular Engineering
- 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)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1470029
- Grant/Contract Number:
- SC0012577
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 50; Journal Issue: 23; Related Information: UNCAGE-ME partners with Georgia Institute of Technology (lead); Lehigh University; Oak Ridge National Laboratory; University of Alabama; University of Florida; University of Wisconsin; Washington University in St. Louis; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; 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., and Jones, Christopher W. Insights into Azetidine Polymerization for the Preparation of Poly(propylenimine)-Based CO2 Adsorbents. United States: N. p., 2017.
Web. doi:10.1021/acs.macromol.7b02402.
Sarazen, Michele L., & Jones, Christopher W. Insights into Azetidine Polymerization for the Preparation of Poly(propylenimine)-Based CO2 Adsorbents. United States. https://doi.org/10.1021/acs.macromol.7b02402
Sarazen, Michele L., and Jones, Christopher W. Tue .
"Insights into Azetidine Polymerization for the Preparation of Poly(propylenimine)-Based CO2 Adsorbents". United States. https://doi.org/10.1021/acs.macromol.7b02402. https://www.osti.gov/servlets/purl/1470029.
@article{osti_1470029,
title = {Insights into Azetidine Polymerization for the Preparation of Poly(propylenimine)-Based CO2 Adsorbents},
author = {Sarazen, Michele L. and Jones, Christopher W.},
abstractNote = {The cationic ring-opening polymerization of azetidine to form branched poly(propylenimine) (PPI) is investigated for the purpose of evaluating the utility of PPI/silica composite adsorbents for CO2 capture. The polymerization kinetics and primary:secondary:tertiary amine distribution are monitored with 1H NMR during reaction with varied synthesis conditions (i.e., reaction time 20–150 h), temperature (343–353 K), and monomer to acid initiator (here, HClO4) ratio. It is found that primary amines are converted to tertiary amines with increased polymerization time, while the addition of monomer over the first 6 h of polymerization increases the primary amine content. This suggests a mechanism where the monomer is rapidly consumed, leaving dimers or small oligomers that still contain rings as key reaction centers. The synthesized polymer is neutralized with either NH4OH or a basic resin and impregnated into mesoporous silica (SBA-15). The CO2 capture properties of these composite adsorbents are investigated, giving information about the effectiveness of the acid neutralization processes.},
doi = {10.1021/acs.macromol.7b02402},
journal = {Macromolecules},
number = 23,
volume = 50,
place = {United States},
year = {Tue Nov 21 00:00:00 EST 2017},
month = {Tue Nov 21 00:00:00 EST 2017}
}
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