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@ARTICLE{Krutyeva:279669,
author = {Krutyeva, M. and Bras, Ana and Antonius, W. and Hövelmann,
Claas and Poulos, A. S. and Allgaier, J. and Radulescu, A.
and Lindner, P. and Pyckhout-Hintzen, W. and Wischnewski, A.
and Richter, D.},
title = {{A}ssociation {B}ehavior, {D}iffusion, and {V}iscosity of
{E}nd-{F}unctionalized {S}upramolecular {P}oly(ethylene
glycol) in the {M}elt {S}tate},
journal = {Macromolecules},
volume = {48},
number = {24},
issn = {1520-5835},
address = {Washington, DC},
publisher = {Soc.},
reportid = {FZJ-2015-07551},
pages = {8933–8946},
year = {2015},
abstract = {In this work we present a combined analysis of small-angle
neutron scattering, linear rheology and pulsed field
gradient nuclear magnetic resonance spectroscopy experiments
on the supramolecular association and chain structure of
well-defined telechelically modified poly(ethylene glycol)
(PEG) in the bulk. Oligomeric PEG was functionalized with
directed heterocomplementary hydrogen-bonding end-groups,
thymine (Thy) and diaminotriazine (DAT). The polarity of the
backbone polymer is comparable to the end groups and avoids
clustering of the groups basing on energetic arguments.
Their linear association behavior in the ideal melt state
was investigated on the microscopic/molecular level as a
function of temperature. By means of a selective labeling
scheme, which should ideally lead to the formation of
alternating hydrogeneous-deuterated building block sequences
if the hydrogen bonding reaction is exclusively
heterocomplementary, we showed that the Thy–DAT
association is dominant and a Thy–Thy homoassociation is
approximately three times less probable. Latter nondirected
association gives rise to a considerable amount of
random-copolymerization without affecting seriously neither
the macroscopic melt viscosity nor the diffusivity of the
supramolecular associates. From the q-dependence of a
multiblock RPA structure factor, the linear association in
the melt is confirmed. Furthermore, this diffusion and
viscosity study reveals simple Rouse dynamics of
supramolecular polymer chains with molecular weight much
larger than the entanglement mass Me. The Rouse-like
dynamics of long supramolecular chains indicates short
lifetime hydrogen bonds of the end groups. Our results are
in excellent agreement with the related polycondensation
theory.},
cin = {ICS-1 / Neutronenstreuung ; JCNS-1 / JCNS (München) ;
Jülich Centre for Neutron Science JCNS (München) ;
JCNS-FRM-II},
ddc = {540},
cid = {I:(DE-Juel1)ICS-1-20110106 / I:(DE-Juel1)JCNS-1-20110106 /
I:(DE-Juel1)JCNS-FRM-II-20110218},
pnm = {551 - Functional Macromolecules and Complexes (POF3-551) /
6G4 - Jülich Centre for Neutron Research (JCNS) (POF3-623)
/ 6215 - Soft Matter, Health and Life Sciences (POF3-621)},
pid = {G:(DE-HGF)POF3-551 / G:(DE-HGF)POF3-6G4 /
G:(DE-HGF)POF3-6215},
experiment = {EXP:(DE-MLZ)KWS2-20140101},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000367279500028},
doi = {10.1021/acs.macromol.5b02060},
url = {https://juser.fz-juelich.de/record/279669},
}