TY - JOUR
T1 - Thermal and Gas Adsorption Properties of Tröger's Base/Diazacyclooctane Hybrid Ladder Polymers
AU - Inoue, Keiki
AU - Selyanchyn, Roman
AU - Fujikawa, Shigenori
AU - Ishiwari, Fumitaka
AU - Fukushima, Takanori
N1 - Funding Information:
This work was supported by KAKENHI (Grant‐in‐Aids for Young Scientists B No. 26810067, Young Scientists A No. 17H04879, Scientific Research on Innovative Areas “Coordination Asymmetry” No. 19H04567, Scientific Research B No. 20H02784), JST CREST (JPMJCR18I4) Japan, Grant‐in‐Aid for 2018 DAICEL Award in Synthetic Organic Chemistry, Japan, Grant‐in‐Aid for Young Scientists from the Japan Prize Foundation, Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials from the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT) and “Moonshot Research and Development Program” (JPNP18016) commissioned by the New Energy and Industrial Technology Development Organization (NEDO) No. JPNP18016. We thank Materials Analysis Division, Open Facility Center, Tokyo Institute of Technology, for the support on the NMR and SEC‐MALS measurements.
Funding Information:
This work was supported by KAKENHI (Grant-in-Aids for Young Scientists B No. 26810067, Young Scientists A No. 17H04879, Scientific Research on Innovative Areas ?Coordination Asymmetry? No. 19H04567, Scientific Research B No. 20H02784), JST CREST (JPMJCR18I4) Japan, Grant-in-Aid for 2018 DAICEL Award in Synthetic Organic Chemistry, Japan, Grant-in-Aid for Young Scientists from the Japan Prize Foundation, Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials from the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT) and ?Moonshot Research and Development Program? (JPNP18016) commissioned by the New Energy and Industrial Technology Development Organization (NEDO) No. JPNP18016. We thank Materials Analysis Division, Open Facility Center, Tokyo Institute of Technology, for the support on the NMR and SEC-MALS measurements.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2021/4/26
Y1 - 2021/4/26
N2 - A polymer of intrinsic microporosity (PIM) consisting of Tröger's base (TB) undergoes ring opening of the bicyclic amine upon N-methylation followed by alkaline hydrolysis, resulting in a hybrid ladder polymer that contains diazacyclooctane (DACO) units with tert- and sec-amino groups. The hybrid ladder polymers with various TB/DACO ratios can be prepared depending on the reaction conditions. Here we report a systematic study on the effect of DACO content on the thermal and gas adsorption properties of the hybrid ladder polymer. Using a PIM derived from 2,5-diamino-p-xylene, we prepared hybrid ladder polymers with a DACO content ranging from 19% to 55% while having a similar molecular weight. The thermal stability of the hybrid ladder polymers, evaluated by thermogravimetric analysis, is decreased with the increase in DACO content. Based on gas adsorption measurements, the increase in DACO content results in the decrease in the BET surface area but improves the gas adsorption selectivity for CO2 against N2, likely due to high basicity of the sec-amino group of DACO unit. This result demonstrates that the partial TB-to-DACO conversion of the TB-based PIM may provide a simple but useful strategy to design polymer materials that enable selective CO2 capture and/or separation.
AB - A polymer of intrinsic microporosity (PIM) consisting of Tröger's base (TB) undergoes ring opening of the bicyclic amine upon N-methylation followed by alkaline hydrolysis, resulting in a hybrid ladder polymer that contains diazacyclooctane (DACO) units with tert- and sec-amino groups. The hybrid ladder polymers with various TB/DACO ratios can be prepared depending on the reaction conditions. Here we report a systematic study on the effect of DACO content on the thermal and gas adsorption properties of the hybrid ladder polymer. Using a PIM derived from 2,5-diamino-p-xylene, we prepared hybrid ladder polymers with a DACO content ranging from 19% to 55% while having a similar molecular weight. The thermal stability of the hybrid ladder polymers, evaluated by thermogravimetric analysis, is decreased with the increase in DACO content. Based on gas adsorption measurements, the increase in DACO content results in the decrease in the BET surface area but improves the gas adsorption selectivity for CO2 against N2, likely due to high basicity of the sec-amino group of DACO unit. This result demonstrates that the partial TB-to-DACO conversion of the TB-based PIM may provide a simple but useful strategy to design polymer materials that enable selective CO2 capture and/or separation.
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U2 - 10.1002/cnma.202100151
DO - 10.1002/cnma.202100151
M3 - Article
AN - SCOPUS:85105383689
SN - 2199-692X
VL - 7
SP - 824
JO - ChemNanoMat
JF - ChemNanoMat
IS - 7
ER -
