University of Groningen
Dynamics and self-assembly in architecturally complex supramolecular polymers
Golkaram, Milad
DOI:
10.33612/diss.126818904
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Publication date: 2020
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Golkaram, M. (2020). Dynamics and self-assembly in architecturally complex supramolecular polymers. University of Groningen. https://doi.org/10.33612/diss.126818904
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Dynamics and self-assembly in
architecturally complex
supramolecular polymers
Dynamics and self-assembly in architecturally complex supramolecular
polymers
Milad Golkaram
PhD thesis
University of Groningen
The Netherlands
Zernike Institute PhD thesis series 2020-09
ISSN: 1570-1530
ISBN: 978-94-034-2647-1 (Printed version)
ISBN: 978-94-034-2646-4 (Electronic version)
The research presented in this thesis was performed in the research group of
Macromolecular Chemistry and New Polymeric Materials of the Zernike Institute
for Advanced Materials at the University of Groningen, The Netherlands. This
work was financially supported by the Innovation Research Incentives Scheme
of Dutch Research Council NWO (VICI Grant 724.013.001).
Cover design by Milad Golkaram
Dutch summary by Albert J.J. Woortman
Printed by ProefschriftMaken || www.proefschriftmaken.nl
ã
Milad Golkaram
All right reserved. Save exceptions stated by the law, no part of this publication
may be reproduced in any form, by print, photocopying, or otherwise, without the
prior written permission from the author.
Dynamics and self-assembly in
architecturally complex
supramolecular polymers
Proefschrift
ter verkrijging van de graad van doctor aan de
Rijksuniversiteit Groningen
op gezag van de
rector magnificus prof. dr. C. Wijmenga
en volgens besluit van het College voor Promoties.
De openbare verdediging zal plaatsvinden op
maandag 15 juni 2020 om 14:30 uur
door
Milad Golkaram
geboren op 29 augustus 1990
te Tehran, Iran
Promotores
Prof. dr. K.U. Loos
Prof. dr. E. van Ruymbeke
Beoordelingscommissie
Prof. dr. F. Picchioni
Prof. dr. M. M. G. Kamperman
Prof. dr. W. H. Binder
Contents
Chapter 1:
Introduction: A Critical Approach to Polymer Dynamics in
Supramolecular Polymers ... 5
1.1 ABSTRACT ... 5
1.2 INTRODUCTION ... 6
1.3 ASSOCIATION NUMBER PER STICKER ... 7
1.4 PHASE SEPARATION ... 9
1.5 ASSOCIATION STRENGTH ... 15
1.6 STICKER POSITION ... 20
1.6.1 In the Main Chain. ... 21
1.6.2 UPy as Side Groups. ... 24
1.6.3 Other Side Groups. ... 28
1.6.4 Miscellaneous. ... 29
1.7 OUTLOOK ... 35
1.8 CONCLUDING REMARKS ... 36
1.9 Aim and outline of the thesis ... 36
1.10 REFERENCES... 37
Chapter 2:
Linear Viscoelasticity of Weakly Hydrogen-Bonded Polymers
near and below the Sol−Gel Transition ... 51
2.1 ABSTRACT ... 51 2.2 INTRODUCTION ... 52 2.3 BACKGROUND ... 53 2.4 EXPERIMENTAL SECTION ... 55 2.4.1 Materials. ... 55 2.4.2 Synthesis of PTHYi. ... 55 2.4.3 Characterization. ... 56
2.5 RESULTS AND DISCUSSION ... 56
2.6 CONCLUSION ... 65
2.7 REFERENCES... 66
Chapter 3:
Supramolecular Mimic for Bottlebrush Polymers in Bulk ... 69
3.1 ABSTRACT ... 70
3.2 INTRODUCTION ... 71
3.3 EXPERIMENTAL SECTION ... 72
3.3.1 Materials. ... 72
3.3.2 Characterization. ... 72
3.3.3 Synthesis of Poly(tetrahydrofuran)s (PTHFs) 1a−d. ... 74
3.3.4 Synthesis of 1-(6-Isocyanatohexyl)-3-(7-oxo-7,8-dihydro-1,8-naphthyridin-2-yl)urea 2 (ODIN). ... 74
3.3.5 Synthesis of 1-(6-Isocyanatohexyl)-3-(7-oxo-7,8-dihydro-1,8-naphthyridin-2-yl)urea-PTHF (3a−d). ... 75
3.3.6 Synthesis of PTHF-UPy (3e). ... 75
3.4 RESULTS AND DISCUSSION ...76
3.4.1 Synthesis of Poly(tetrahydrofuran)s (PTHFs) (1a−d). ...76
3.4.2 Self-Assembly Studies. ...79
3.4.3 Small-Angle X-ray Scattering (SAXS). ...90
3.4.4 Melt Rheology. ...92
3.5 CONCLUSIONS ...98
3.6 REFERENCES ...99
Chapter 4:
Order-Disorder Transition in Supramolecular Polymer
Combs/Brushes with Polymeric Side Chains ... 105
4.1 ABSTRACT ...105 4.2 INTRODUCTION ...106 4.3 EXPERIMENTAL SECTION ...108 4.3.1 Materials. ...108 4.3.2 Characterization. ...108 4.3.3 Synthesis of CTA-UPy 3. ...109 4.3.4 Synthesis of CTA-DAT 6. ...110
4.3.5 RAFT polymerization of n-butyl acrylate using UPy 3 or CTA-DAT 6. ...110
4.3.6 Synthesis of PnBa 9. ...111
4.3.7 Synthesis of ((1-(6-Isocyanatohexyl)-3-(7-oxo-7,8-dihydro-1,8-naphthyridin-2-yl)urea) (ODIN)) 10. ...111
4.3.8 Synthesis of polymer OD. ...112
4.3.9 Synthesis of 2-(((6-(3-(7-oxo-7,8-dihydro-1,8-naphthyridin-2-yl)ureido)hexyl)carbamoyl)oxy)ethyl acrylate 12. ...112
4.3.10 RAFT polymerization of acrylate 12. ...113
4.4 RESULTS AND DISCUSSION ...113
4.4.1 Synthesis of polymers. ...113
4.4.2 Small angle X-ray scattering (SAXS) ...123
4.4.3 Melt Rheology ...131
4.5 CONCLUSIONS ...133
4.6 REFERENCES ...134
Chapter 5:
Origin of the Linear Viscoelastic Behavior in Supramolecular
Polymer Brushes: Effect of Molecular Weight and Crosslinking on Colloidal
Properties
... 139
5.1 ABSTRACT ...139 5.2 INTRODUCTION ...140 5.3 EXPERIMENTAL SECTION ...142 5.3.1 Materials. ...142 5.3.2 Characterization. ...1425.3.3 Synthesis of poly(methyl acrylate)s (PmA)...143
5.3.4 Synthesis of ((1-(6-Isocyanatohexyl)-3-(7-oxo-7,8-dihydro-1,8-naphthyridin-2-yl)urea) (ODIN)). ...143
5.3.5 Synthesis of PmA-ODINs. ...144
5.3.6 Synthesis of PEG-ODINs. ...144
5.3.7 Synthesis of PDMS-ODIN. ...144
5.4 RESULTS AND DISCUSSION ...145
5.4.1 Polymer synthesis. ...145
5.4.3 Rheology: effect of crosslinking. ... 159
5.4.4 Rheology: effect of chemistry. ... 167
5.5 CONCLUSIONS ... 168
5.6 REFERENCES... 169
