Ring-closure and ring-expansion techniques are the two routes for extensive synthesis of cyclic polymers. Here, we report an alternative blocking-cyclization technique referred to as the third route to prepare cyclic polymers with regulated ring size and ring number by ring-opening metathesis polymerization of di- and monofunctional monomers in a one-pot process, where the polymer intermediates bearing two single-stranded blocks are efficiently cyclized by the cyclizing unit of propagated ladderphane to generate corresponding mono-, bis-, and tricyclic polymers, and the well-defined ladderphane structure plays a crucial role in forming the cyclic topology. Monocyclic polymer is further modified via Alder-ene reaction and the cyclic molecular topology is clearly demonstrated. The diversity features of cyclic polymers are comprehensively revealed. This strategy has broken through the limitations of previous two cyclizing routes, and indeed opens a facile and popular way to various cyclic polymers by commercial Grubbs catalyst and conventional metathesis polymerization.
Eucommia ulmoides gum (EUG) was applied in blend rubber with a heavily limited amount because of its duality of rubber and plastic, and an efficient way of triazolinedione (TAD)-based Alder-ene reaction was used to improve the elastic properties of EUG. Binary modification of EUG with two TADs containing hexyl and polyhedral oligomeric silsesquioxane (POSS) groups were conducted to generate the modified EUG elastomers with tunable mechanical properties and good compatibility by varying TAD contents. When the low hexyl (1%) and POSS (0.2%) TADs incorporated, the modified EUGs displayed high tensile strength of 36.57 MPa with the elongation at break of 876%, and thus high toughness of 152.14 MJ m −3 . If high contents of hexyl (20%) and POSS (0.2%) TADs employed, the modified EUGs exhibited excellent elongation at break of 1165% and recovery rate of 60%, and especially its loss factor reached up to 0.83-0.65 at 20-70 C. Therefore, the modified EUGs containing the polar urazole and POSS groups should be a novel elastomer with good compatibility, wear resistance, and damping properties.
A trifunctional diyne comonomer can regulate the structure and optimize the physical state of polyacetylene ionomers, which exhibit a high ionic conductivity of 2.6 × 10−5–1.0 × 10−3 S cm−1 at 30 °C.
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