Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers
The macromolecular dynamics of dendronized copolymer membranes (PECHs), obtained by chemical modification of poly(epichlorohydrin) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, was investigated. In response to a thermal treatment during membrane preparation, these copolymers...
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MDPI AG
2021-06-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/13/12/1961 |
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| author | R. Teruel-Juanes B. Pascual-Jose R. Graf J. A. Reina M. Giamberini A. Ribes-Greus |
| author_facet | R. Teruel-Juanes B. Pascual-Jose R. Graf J. A. Reina M. Giamberini A. Ribes-Greus |
| author_sort | R. Teruel-Juanes |
| collection | DOAJ |
| description | The macromolecular dynamics of dendronized copolymer membranes (PECHs), obtained by chemical modification of poly(epichlorohydrin) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, was investigated. In response to a thermal treatment during membrane preparation, these copolymers show an ability to change their shape, achieve orientation, and slightly crystallize, which was also observed by CP-MAS NMR, XRD, and DSC. The phenomenon was deeply analyzed by dielectric thermal analysis. The dielectric spectra show the influence of several factors such as the number of dendritic side groups, the orientation, their self-assembling dendrons, and the molecular mobility. The dielectric spectra present a sub-Tg dielectric relaxation, labelled as γ, associated with the mobility of the benzyloxy substituent of the dendritic group. This mobility is not related to the percentage of these lateral chains but is somewhat hindered by the orientation of the dendritic groups. Unlike other less complex polymers, the crystallization was dismantled before the appearance of the glass transition (α<sub>Tg</sub>). Only after that, clearing transition (α<sub>Clear</sub>) can be observed. The PECHs were flexible and offered a high free volume, despite presenting a high degree of modifications. However, the molecular mobility is not independent in each phase and the self-assembling dendrons can be eventually fine-tuned according to the percentage of grafted groups. |
| first_indexed | 2024-03-10T10:26:04Z |
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| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T10:26:04Z |
| publishDate | 2021-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-1beb7f7d9ef24810808bc963d24871c52023-11-21T23:57:10ZengMDPI AGPolymers2073-43602021-06-011312196110.3390/polym13121961Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) CopolymersR. Teruel-Juanes0B. Pascual-Jose1R. Graf2J. A. Reina3M. Giamberini4A. Ribes-Greus5Institute of Technology of Materials (ITM), Universitat Politècnica de València (UPV), Camí de Vera s/n, 46022 Valencia, SpainInstitute of Technology of Materials (ITM), Universitat Politècnica de València (UPV), Camí de Vera s/n, 46022 Valencia, SpainMax Planck Institute for Polymer Research, Ackermannweg 10, Postfach 3148, 55021 Mainz, GermanyDepartment of Analytical Chemistry and Organic Chemistry, Universitat Rovira I Virigili (URV), C/Marcel·lí Domingo s/n, 43007 Tarragona, SpainDepartment of Chemical Engineering (DEQ), Universitat Rovira I Virgili (URV), Av. Païssos Catalans 26, 43007 Tarragona, SpainInstitute of Technology of Materials (ITM), Universitat Politècnica de València (UPV), Camí de Vera s/n, 46022 Valencia, SpainThe macromolecular dynamics of dendronized copolymer membranes (PECHs), obtained by chemical modification of poly(epichlorohydrin) with the dendron 3,4,5-tris[4-(n-dodecan-1-yloxy)benzyloxy] benzoate, was investigated. In response to a thermal treatment during membrane preparation, these copolymers show an ability to change their shape, achieve orientation, and slightly crystallize, which was also observed by CP-MAS NMR, XRD, and DSC. The phenomenon was deeply analyzed by dielectric thermal analysis. The dielectric spectra show the influence of several factors such as the number of dendritic side groups, the orientation, their self-assembling dendrons, and the molecular mobility. The dielectric spectra present a sub-Tg dielectric relaxation, labelled as γ, associated with the mobility of the benzyloxy substituent of the dendritic group. This mobility is not related to the percentage of these lateral chains but is somewhat hindered by the orientation of the dendritic groups. Unlike other less complex polymers, the crystallization was dismantled before the appearance of the glass transition (α<sub>Tg</sub>). Only after that, clearing transition (α<sub>Clear</sub>) can be observed. The PECHs were flexible and offered a high free volume, despite presenting a high degree of modifications. However, the molecular mobility is not independent in each phase and the self-assembling dendrons can be eventually fine-tuned according to the percentage of grafted groups.https://www.mdpi.com/2073-4360/13/12/1961broadband dielectric spectroscopydielectric relaxation spectramacromolecular cooperativitysegmental dynamicsdendronized liquid crystal membranespoly(epichlorohydrin) |
| spellingShingle | R. Teruel-Juanes B. Pascual-Jose R. Graf J. A. Reina M. Giamberini A. Ribes-Greus Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers Polymers broadband dielectric spectroscopy dielectric relaxation spectra macromolecular cooperativity segmental dynamics dendronized liquid crystal membranes poly(epichlorohydrin) |
| title | Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers |
| title_full | Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers |
| title_fullStr | Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers |
| title_full_unstemmed | Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers |
| title_short | Effect of Dendritic Side Groups on the Mobility of Modified Poly(epichlorohydrin) Copolymers |
| title_sort | effect of dendritic side groups on the mobility of modified poly epichlorohydrin copolymers |
| topic | broadband dielectric spectroscopy dielectric relaxation spectra macromolecular cooperativity segmental dynamics dendronized liquid crystal membranes poly(epichlorohydrin) |
| url | https://www.mdpi.com/2073-4360/13/12/1961 |
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