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| 001 | 894130 | ||
| 005 | 20210810182028.0 | ||
| 024 | 7 | _ | |a 10.3390/polym13142235 |2 doi |
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| 100 | 1 | _ | |a Bras, Ana |0 P:(DE-Juel1)140548 |b 0 |e Corresponding author |
| 245 | _ | _ | |a Chain-End Effects on Supramolecular Poly(ethylene glycol) Polymers |
| 260 | _ | _ | |a Basel |c 2021 |b MDPI |
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| 520 | _ | _ | |a In this work we present a fundamental analysis based on small-angle scattering, linear rheology and differential scanning calorimetry (DSC) experiments of the role of different hydrogen bonding (H-bonding) types on the structure and dynamics of chain-end modified poly(ethylene glycol) (PEG) in bulk. As such bifunctional PEG with a molar mass below the entanglement mass Me is symmetrically end-functionalized with three different hydrogen bonding (H-bonding) groups: thymine-1-acetic acid (thy), diamino-triazine (dat) and 2-ureido-4[1H]-pyrimidinone (upy). A linear block copolymer structure and a Newtonian-like dynamics is observed for PEG-thy/dat while results for PEG-upy structure and dynamics reveal a sphere and a network-like behavior, respectively. These observations are concomitant with an increase of the Flory–Huggins interaction parameter from PEG-thy/dat to PEG-upy that is used to quantify the difference between the H-bonding types. The upy association into spherical clusters is established by the Percus–Yevick approximation that models the inter-particle structure factor for PEG-upy. Moreover, the viscosity study reveals for PEG-upy a shear thickening behavior interpreted in terms of the free path model and related to the time for PEG-upy to dissociate from the upy clusters, seen as virtual crosslinks of the formed network. Moreover, a second relaxation time of different nature is also obtained from the complex shear modulus measurements of PEG-upy by the inverse of the angular frequency where G’ and G’’ crosses from the network-like to glass-like transition relaxation time, which is related to the segmental friction of PEG-upy polymeric network strands. In fact, not only do PEG-thy/dat and PEG-upy have different viscoelastic properties, but the relaxation times found for PEG-upy are much slower than the ones for PEG-thy/dat. However, the activation energy related to the association dynamics is very similar for both PEG-thy/dat and PEG-upy. Concerning the segmental dynamics, the glass transition temperature obtained from both rheological and calorimetric analysis is similar and increases for PEG-upy while for PEG-thy/dat is almost independent of association behavior. Our results show how supramolecular PEG properties vary by modifying the H-bonding association type and changing the molecular Flory–Huggins interaction parameter, which can be further explored for possible applications |
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| 693 | _ | _ | |a Forschungs-Neutronenquelle Heinz Maier-Leibnitz |e KWS-2: Small angle scattering diffractometer |f NL3ao |1 EXP:(DE-MLZ)FRMII-20140101 |0 EXP:(DE-MLZ)KWS2-20140101 |5 EXP:(DE-MLZ)KWS2-20140101 |6 EXP:(DE-MLZ)NL3ao-20140101 |x 0 |
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| 773 | _ | _ | |a 10.3390/polym13142235 |g Vol. 13, no. 14, p. 2235 - |0 PERI:(DE-600)2527146-5 |n 14 |p 2235 |t Polymers |v 13 |y 2021 |x 2073-4360 |
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