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
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr. 29, 119991 Moscow, Russia.
Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, 119071 Moscow, Russia.
Polymers (Basel). 2021 May 27;13(11):1756. doi: 10.3390/polym13111756.
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.
我们研究了在第一代格拉布催化剂存在下，通过无定形聚降冰片烯与半结晶聚十二碳烯之间的大分子交叉复分解反应合成的降冰片烯与环十二碳烯多嵌段共聚物的结构-性能关系。通过调整反应时间、催化剂量和初始体系的组成，我们得到了一组统计多嵌段共聚物，它们在降冰片烯和十二碳烯单元序列的组成和平均长度上有所不同。利用核磁共振（NMR）、X射线衍射（XRD）、差示扫描量热法（DSC，包括连续自核化和退火的热分级）以及旋转流变学对共聚物进行结构、热性能和力学性能表征，使我们能够将反应条件与可结晶单元序列的平均长度、相应片晶的厚度及其熔点联系起来。我们证明，孤立的十二碳烯单元可以并入结晶片晶中，因此即使是近乎无规的共聚物也应保持结晶性。在降冰片烯与环十二碳烯及其他环烯烃的多嵌段共聚物中观察到的微弱高温吸热峰可能表明相应体系在熔融状态下发生了微相分离。
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