% IMPORTANT: The following is UTF-8 encoded. This means that in the presence
% of non-ASCII characters, it will not work with BibTeX 0.99 or older.
% Instead, you should use an up-to-date BibTeX implementation like “bibtex8” or
% “biber”.
@ARTICLE{Staropoli:821019,
author = {Staropoli, Mariapaola and Raba, Andreas and Hövelmann,
Claas H. and Krutyeva, Margarita and Allgaier, J. and
Appavou, Marie-Sousai and Keiderling, Uwe and Stadler,
Florian J. and Pyckhout-Hintzen, Wim and Wischnewski,
Andreas and Richter, Dieter},
title = {{H}ydrogen {B}onding in a {R}eversible {C}omb {P}olymer
{A}rchitecture: {A} {M}icroscopic and {M}acroscopic
{I}nvestigation},
journal = {Macromolecules},
volume = {49},
number = {15},
issn = {1520-5835},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2016-06276},
pages = {5692 - 5703},
year = {2016},
abstract = {In this work, an investigation of the hydrogen-bonding
mechanism in a transiently branched comb-like polymer system
in the melt is reported. The system under investigation
consists of a polybutylene oxide (PBO)-based backbone,
randomly functionalized with thymine (thy) groups, in
combination with shorter PBO graft chains,
end-functionalized with diaminotriazine (DAT) groups. The
functional groups are able to associate through hydrogen
bonding. The heterocomplementary association of these groups
leads to the formation of a transiently branched comb-like
polymer system. Since recently virtually exclusive
heterocomplementary association could be observed in the
supramolecular association of telechelically modified
oligomeric PEG chains, here we aim to extend the
supramolecular assembly mechanism toward branched
structures. The present work combines small angle neutron
scattering (SANS) experiments on a selectively labeled
system with macroscopic dynamics measured in linear rheology
response. The association of thy- and DAT-modified
components was studied as a function of temperature and
composition. The scattering function reveals the formation
of a block copolymer and can be exclusively attributed to
heterocomplementary association of the hydrogen-bonding
groups. Scattering functions of nonfunctionalized blends are
also reported as references and evidence the change in the
microstructure induced by the heterocomplementary
association. All scattering profiles were described by means
of the random phase approximation (RPA) formalism from which
the average aggregation number, i.e., comb arm functionality
and the equilibrium association constant could be determined
directly in the melt state as a function of temperature. On
the other hand, rheological measurements were performed in
the melt state to study the influence of the reversible
bonds on the macroscopic dynamics of the polymer system. The
rheology data are in good agreement with the SANS results
and confirm the transient comb-like branched architecture.
The supramolecular association exhibits characteristic
bonding times of the groups in the order of 1 s at −25 °C
and therefore makes the thy–DAT pair an ideal candidate
for the development of responsive materials that combine
permanent and transient linkages for novel applications and
self-healing properties.},
cin = {JCNS (München) ; Jülich Centre for Neutron Science JCNS
(München) ; JCNS-FRM-II / Neutronenstreuung ; JCNS-1 /
JCNS-2},
ddc = {540},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-1-20110106 / I:(DE-Juel1)JCNS-2-20110106},
pnm = {6215 - Soft Matter, Health and Life Sciences (POF3-621) /
6G15 - FRM II / MLZ (POF3-6G15) / 6G4 - Jülich Centre for
Neutron Research (JCNS) (POF3-623)},
pid = {G:(DE-HGF)POF3-6215 / G:(DE-HGF)POF3-6G15 /
G:(DE-HGF)POF3-6G4},
experiment = {EXP:(DE-MLZ)KWS2-20140101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000381320300039},
doi = {10.1021/acs.macromol.6b00978},
url = {https://juser.fz-juelich.de/record/821019},
}