Multiblock Copolymers of Norbornene and Cyclododecene: Chain Structure and Properties

We investigate the structure-property relations of the multiblock copolymers of norbornene with cyclododecene synthesized via the macromolecular cross-metathesis reaction between amorphous polynorbornene and semicrystalline polydodecenamer in the presence of the first-generation Grubbs catalyst. By...

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Published inPolymers Vol. 13; no. 11; p. 1756
Main Authors Denisova, Yulia I, Shandryuk, Georgiy A, Arinina, Marianna P, Levin, Ivan S, Zhigarev, Vsevolod A, Gringolts, Maria L, Finkelshtein, Eugene Sh, Malkin, Alexander Ya, Kudryavtsev, Yaroslav V
Format Journal Article
LanguageEnglish
Published Switzerland MDPI AG 27.05.2021
MDPI
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Summary:We investigate the structure-property relations of the multiblock copolymers of norbornene with cyclododecene synthesized via the macromolecular cross-metathesis reaction between amorphous polynorbornene and semicrystalline polydodecenamer in the presence of the first-generation Grubbs catalyst. By adjusting the reaction time, catalyst amount, and composition of the initial system, we obtain a set of statistical multiblock copolymers that differ in the composition and average length of norbornene and dodecenylene unit sequences. Structural, thermal, and mechanical characterization of the copolymers with NMR, XRD, DSC (including thermal fractionation by successive self-nucleation and annealing), and rotational rheology allows us to relate the reaction conditions to the average length of crystallizable unit sequences, thicknesses of corresponding lamellas, and temperatures of their melting. We demonstrate that isolated dodecenylene units can be incorporated into crystalline lamellas so that even nearly random copolymers should retain crystallinity. Weak high-temperature endotherms observed in the multiblock copolymers of norbornene with cyclododecene and other cycloolefins could indicate that the corresponding systems are microphase-separated in the melt state.
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ISSN:2073-4360
2073-4360
DOI:10.3390/polym13111756