Chemistry of Materials
Article
Hyperbranched Poly(propylenimine)-Oxide Hybrid.
Polyamines with different lengths of methylene spacers
between the amine groups may affect the material stability
and performance in some applications such as catalysis and
CO2 capture. A SBA-15-supported poly(propylenimine)
material was also prepared via the vapor-phase transport
using azetidine monomer (see Scheme 1) with an azetidine/
SBA-15 mass ratio of 4 at 80 °C for 24 h. The polyamine
loading was calculated from the TGA weight loss to be about
ASSOCIATED CONTENT
Supporting Information
Experimental setup, detailed characterizations of the SBA-15,
Al-grafted SBA-15, and alumina supports, FE-SEM images and
differential TGA curves of the hybrids, and XRD pattern,
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*
S
2
f
differential TGA curve, N sorption isotherms and NL-DFT
2
pore size distribution of the hyperbranched poly-
15 wt %. The powder XRD pattern of the resulting material
(
see Supporting Information, Figure S7a) indicates that the 2D
AUTHOR INFORMATION
Present Address
World Premier International (WPI) Research Center for
Materials Nanoarchitectonics (MANA), National Institute for
Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044
Japan.
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hexagonal mesostructure of the material was maintained, as in
the case of materials made with aziridine. The DTG curve
depicted in the Supporting Information, Figure S7b, shows a
peak at 245 °C, which is 25 °C higher than the peaks seen in
the supported poly(ethylenimine) materials, suggesting the
supported poly(propylenimine) is thermally more stable than
its poly(ethylenimine) counterparts. Nitrogen adsorption−
desorption isotherms and the corresponding NL-DFT pore
size distribution are shown in the Supporting Information,
Figures S7c and S7d, respectively. The BET surface area and
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†
Notes
The authors declare the following competing financial
interest(s): C.W.J. has a financial interest in Global Thermostat,
LLC.
2
−1
total pore volume were calculated to be 334 m g and 0.68
cm g , respectively. The resulting poly(propylenimine)
hybrid material had lower organic loading than the poly-
3
−1
ACKNOWLEDGMENTS
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(
ethylenimine) material prepared under the same conditions,
We thank Global Thermostat, LLC and School of Chemical &
Biomolecular Engineering at Georgia Tech (through the New-
Vision Professorship awarded to C.W.J) for financial support.
most likely because azetidine has a lower vapor pressure (i.e.,
higher boiling point) and less ring strain than aziridine. The
loading of the poly(propylenimine) may be improved by
preparing materials at harsher conditions. Optimization of
synthesis conditions to attain higher poly(propylenimine)
loadings merits investigation in future work.
9
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(
̈
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CONCLUSIONS
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Preparation of supported hyperbranched polyamine-oxide
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7
,8,10
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in which the supports are
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dx.doi.org/10.1021/cm303931q | Chem. Mater. 2013, 25, 613−622