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Solid and melt-state 1H NMR studies of relaxation processes in isotactic polypropylenes

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Abstract

Relaxation processes in metallocene and Ziegler–Natta isotactic polypropylenes were studied using 1H MAS NMR spectroscopy. 1H MAS NMR spectra and laboratory-frame spin-lattice relaxation times T 1(1H) were measured within the temperature range 30–190 °C, which covers the glass transition relaxation and melting processes of both polymers. Splitting of the peak related to protons in amorphous regions of the studied samples into three sharp peaks at elevated temperatures made it possible to determine the spin-lattice relaxation times T 1(1H) for particular iPP proton groups. The melt-state NMR spectra of ZN-iPP display three sharp peaks with three additional weak peaks positioned on the less shielded side. Entanglements of ZN-iPP chains are suggested as a possible source of these additional peaks. The spectra of m-iPP indicate substantially fewer entanglements due to its lower molecular weight compared with that of ZN-iPP. The temperature dependences of the relaxation times T 1(1H) relating to specific groups of ZN-iPP were shown to reach minima associated with the motions of amorphous chain segments (glass transition relaxation), which are very close to the melting temperature and minima associated with the melting process. Each of the T 1(1H) temperature dependences for m-iPP shows only one minimum associated with the melting process. When the particular relaxation times T 1, min relating to the minima that occur above the melting temperatures were considered, and these relaxation times were compared for the same proton groups in different samples, significant differences in the relaxation times were observed between samples. Polymer chain motion was more restricted in melted ZN-iPP than in m-iPP, as inferred from the T 1, min values.

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Acknowledgements

This paper was developed as part of the project named “Centre of Excellence for Integrated Research and Exploitation of Advanced Materials and Technologies in Automotive Electronics,” ITMS 26220120055.

One of the authors (IC) gratefully received financial support of this research from the Slovak Research and Development Agency (grant APVV-0226-06).

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Authors and Affiliations

  1. Department of Physics, Faculty of Electrical Engineering and Informatics, Technical University of Košice, Park Komenského 2, 042 00, Košice, Slovakia

    Dušan Olčák, Viktor Hronský, Oľga Fričová, Mária Kovaľaková & Peter Duranka

  2. Polymer Institute, Slovak Academy of Sciences, Dúbravská cesta 9, 845 41, Bratislava, Slovakia

    Ivan Chodák

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  1. Dušan Olčák
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  2. Viktor Hronský
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  3. Oľga Fričová
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  4. Mária Kovaľaková
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  5. Peter Duranka
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  6. Ivan Chodák
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Correspondence to Oľga Fričová.

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Olčák, D., Hronský, V., Fričová, O. et al. Solid and melt-state 1H NMR studies of relaxation processes in isotactic polypropylenes. J Polym Res 20, 117 (2013). https://doi.org/10.1007/s10965-013-0117-5

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