502
L. V. Karabanova et al.
PU’s nanocomposites. This may indicate that hydroxy-POSS could participate in the
reaction of urethane formation using one of the terminal hydroxyl groups, which
allow to be implanted into the chain between cross-links of PU. But with an increase
of POSS amount a certain part of the POSS is not implanted, but plays a role of the
nanofiller in the system.
The dynamic mechanical analysis has shown that the storage moduli of PU/POSS
nanocomposites exceed the storage modulus of PU. But M n /M o changes nonmonotonically with POSS content. The storage moduli of the nanocomposites
increases in 1,5 times compared to the native PU for nanocomposites contained
from 1 to 5 wt% of POSS. Non-monotonic changes of M n /M o may be explained by
the fact (have shown by SAXS investigation) that at 1–5 wt% of POSS, the nanoparticles are chemically implanted into polymer chain. But with an increase of POSS
amount up to 10% a certain part of the POSS is not implanted, but plays a role of the
nanofiller in the system.
From the morphology investigation, it is obvious that POSS introduced into
PU matrix acts as a nanostructuring agent. As a result, the nanocomposites with
more ordered structure are formed thus leading to materials with improved thermal
stability.
References
1. Ray SS, Okamoto M (2003) Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci 28(11):1539–1561. https://doi.org/10.1016/j.progpolym
sci.2003.08.002
2. Shaffer MSP, Sandler JKW (2006) Carbon nanotube/nanofibre polymer composites. In: Advani
SG (ed) Processing and properties of nanocomposites. World Scientific, Singapore
3. Bershtein VA, Gun‘ko VM, Karabanova LV, Sukhanova TE, Yakushev PN, Egorova LM, Turova
AA, Zarko VI, Pakhlov EM, Vylegzhanina ME, Mikhalovsky SV (2013) Polyurethane-poly(2hydroxyethyl methacrylate) semi-IPN-nanooxide composites. RSC Adv 3:14560–14570.
https://doi.org/10.1039/c3ra40295a
4. Karabanova LV, Bershtein VA, Sukhanova TE, Yakushev PN, Egorova LM, Lutsyk
ED, Svyatyna AV, Vylegzhanina ME (2008) 3D diamond-containing nanocomposites
based on hybrid polyurethane–poly(2-hydroxyethyl methacrylate) semi-IPNs: compositionnanostructure-segmental dynamics-elastic properties relationships. J Pol Sci B 46(16):1696–
1712. https://doi.org/10.1002/polb.21506
5. Moniruzzaman M, Winey KI (2006) Polymer nanocomposites containing carbon nanotubes.
Macromolecules 39(16):5194–5205. https://doi.org/10.1021/ma060733p
6. Wolinska-Grabczyk A, Jankowski A (2007) Gas transport properties of segmented
polyurethanes varying in the kind of soft segments. Sep Pur Tech 57(3):413–417. https://
doi.org/10.1016/j.seppur.2006.03.025
7. Gumenna MA, Shevchuk AV, Klimenko NS, Shevchenko VV (2007) Polyurethanes on the
base of polyhedral oligosilsesquioxanes (POSS). Polym J 29(3):177–185 [in Russian]
8. Karabanova LV, Whitby RLD, Bershtein VA, Korobeinyk AV, Yakushev PN, Bondaruk OM,
Lloyd AW, Mikhalovsky SV (2013) The role of interfacial chemistry and interactions in the
dynamics of thermosetting polyurethane-multi-walled carbon nanotube composites with low
filler content. Colloid Polym Sci 291(3):573–583. https://doi.org/10.1007/s00396-012-2745-4
9. Karabanova LV, Whitby RL, Bershtein VA, Korobeinyk AV, Yakushev PN, Bondaruk OM,
Lloyd AW, Mikhalovsky SV (2012) Microstructure changes of polyurethane by inclusion of
L. V. Karabanova et al.
PU’s nanocomposites. This may indicate that hydroxy-POSS could participate in the
reaction of urethane formation using one of the terminal hydroxyl groups, which
allow to be implanted into the chain between cross-links of PU. But with an increase
of POSS amount a certain part of the POSS is not implanted, but plays a role of the
nanofiller in the system.
The dynamic mechanical analysis has shown that the storage moduli of PU/POSS
nanocomposites exceed the storage modulus of PU. But M n /M o changes nonmonotonically with POSS content. The storage moduli of the nanocomposites
increases in 1,5 times compared to the native PU for nanocomposites contained
from 1 to 5 wt% of POSS. Non-monotonic changes of M n /M o may be explained by
the fact (have shown by SAXS investigation) that at 1–5 wt% of POSS, the nanoparticles are chemically implanted into polymer chain. But with an increase of POSS
amount up to 10% a certain part of the POSS is not implanted, but plays a role of the
nanofiller in the system.
From the morphology investigation, it is obvious that POSS introduced into
PU matrix acts as a nanostructuring agent. As a result, the nanocomposites with
more ordered structure are formed thus leading to materials with improved thermal
stability.
References
1. Ray SS, Okamoto M (2003) Polymer/layered silicate nanocomposites: a review from preparation to processing. Prog Polym Sci 28(11):1539–1561. https://doi.org/10.1016/j.progpolym
sci.2003.08.002
2. Shaffer MSP, Sandler JKW (2006) Carbon nanotube/nanofibre polymer composites. In: Advani
SG (ed) Processing and properties of nanocomposites. World Scientific, Singapore
3. Bershtein VA, Gun‘ko VM, Karabanova LV, Sukhanova TE, Yakushev PN, Egorova LM, Turova
AA, Zarko VI, Pakhlov EM, Vylegzhanina ME, Mikhalovsky SV (2013) Polyurethane-poly(2hydroxyethyl methacrylate) semi-IPN-nanooxide composites. RSC Adv 3:14560–14570.
https://doi.org/10.1039/c3ra40295a
4. Karabanova LV, Bershtein VA, Sukhanova TE, Yakushev PN, Egorova LM, Lutsyk
ED, Svyatyna AV, Vylegzhanina ME (2008) 3D diamond-containing nanocomposites
based on hybrid polyurethane–poly(2-hydroxyethyl methacrylate) semi-IPNs: compositionnanostructure-segmental dynamics-elastic properties relationships. J Pol Sci B 46(16):1696–
1712. https://doi.org/10.1002/polb.21506
5. Moniruzzaman M, Winey KI (2006) Polymer nanocomposites containing carbon nanotubes.
Macromolecules 39(16):5194–5205. https://doi.org/10.1021/ma060733p
6. Wolinska-Grabczyk A, Jankowski A (2007) Gas transport properties of segmented
polyurethanes varying in the kind of soft segments. Sep Pur Tech 57(3):413–417. https://
doi.org/10.1016/j.seppur.2006.03.025
7. Gumenna MA, Shevchuk AV, Klimenko NS, Shevchenko VV (2007) Polyurethanes on the
base of polyhedral oligosilsesquioxanes (POSS). Polym J 29(3):177–185 [in Russian]
8. Karabanova LV, Whitby RLD, Bershtein VA, Korobeinyk AV, Yakushev PN, Bondaruk OM,
Lloyd AW, Mikhalovsky SV (2013) The role of interfacial chemistry and interactions in the
dynamics of thermosetting polyurethane-multi-walled carbon nanotube composites with low
filler content. Colloid Polym Sci 291(3):573–583. https://doi.org/10.1007/s00396-012-2745-4
9. Karabanova LV, Whitby RL, Bershtein VA, Korobeinyk AV, Yakushev PN, Bondaruk OM,
Lloyd AW, Mikhalovsky SV (2012) Microstructure changes of polyurethane by inclusion of