Tandem Metathesis Polymerization-Induced Self-Assembly to Nanostructured Block Copolymer and the Controlled Triazolinedione Modification for Enhancing Dielectric Properties

Abstract

The efficient and versatile click chemistry based on 1,2,4-triazoline-3,5-dione (TAD) was used as one of the most potential postfunctionalizing pathways to specially design polymer nanostructure for dielectric materials. The block copolymer was synthesized by tandem ring-opening metathesis polymerization and metathesis cyclopolymerization and self-assembled into the core− shell nanostructure in the selective solvent, which could be modified by TAD in a controlled manner by tuning the TAD feeding amount, enabling the Alder−ene reaction of TAD with the double bonds to occur first on the polynorbornene backbone in the shell and then the cascade Alder−ene and Diels−Alder reactions on the polyacetylene backbone bearing five-membered rings in the core. The modified block copolymers incorporating varied amount of urazole moieties exhibited enhanced dielectric constant from 16.2 to 20.3 and lowered dielectric loss from 0.031 to 0.013 to 0.009, which provides a new idea of the selective postfunctionalization of nanostructures in solution for regulating the polymer structure and properties.

Click chemistry strategies for the accelerated synthesis of functional macromolecules

“…For example, TAD-functionalized fluorinated additives were conjugated on several polydiene backbones (acrylonitrile-butadiene-styrene, styrene-butadiene, and styrene-isoprenestyrene copolymers) to afford superhydrophobicity. 587 Diene-rich polymers synthesized via ADMET 495 and ROMP 588 were also shown to be easily functionalized with substituted TAD compounds efficiently without additives.…”

“…For example, TAD‐functionalized fluorinated additives were conjugated on several polydiene backbones (acrylonitrile–butadiene–styrene, styrene–butadiene, and styrene–isoprene–styrene copolymers) to afford superhydrophobicity 587 . Diene‐rich polymers synthesized via ADMET 495 and ROMP 588 were also shown to be easily functionalized with substituted TAD compounds efficiently without additives. Similarly, a range of unsaturated polyesters, 174,492 poly(glycidyl ether)s 180 and polycarbonates 181 were synthesized by organocatalyzed ROP followed by quantitative and irreversible functionalization with TAD.…”

Direct formation of nano-objects via in situ self-assembly of conjugated polymers

“…Li, Xie, and coworkers also demonstrated the formation of irregularly aggregated micellular structures from PNB6-b-PCPV5 via INCP in chloroform. 52 More uniform structures could be achieved by re-dispersing the nanostructures in THF, suggesting that more uniform nanospheres might have been achieved if THF was used as a polymerization solvent. Xie, Liao, and coworkers also observed self-assembly of PCPV homopolymers into unique structures.…”

Multicomponent Tandem Polymerization of Aromatic Alkynes, Carbonyl Chloride, and Fischer's Base toward Poly(diene merocyanine)s

“…The reported MCPs generally produce non‐conjugated products such as polyamides, polyamines, and poly(ester‐amide)s . To explore the general applicability of MCPs and their polymerization product structures, a popular tandem strategy in organic synthesis has been introduced to MCPs . The multicomponent tandem polymerizations (MCTPs) were developed to synthesize heteroatom or heterocycles‐containing conjugated polymers or sequence‐controlled polymers with well‐defined structures in one pot .…”