Low Length Dispersity Fiber-Like Micelles from an A-B-A Triblock Copolymer with Terminal Crystallizable Poly(ferrocenyldimethylsilane) Segments via Living Crystallization-Driven Self-Assembly

Qiwei Zhang, Horatio He, Alex Oliver, Sam Pearce, Robert Harniman, George Whittell, Yanju Liu, shanyi Du, Jinsong Leng*, Ian Manners

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

1 Citation (Scopus)
43 Downloads (Pure)

Abstract

Solution self-assembly of a linear ABA triblock copolymer with two terminal crystallizable poly(ferrocenyldimethylsilane) (PFS) core-forming "A" blocks and a central poly(dimethylsiloxane) (PDMS) corona-forming "B" block has been investigated. The low dispersity (D = 1.05) copolymer, PFS26-b-PDMS584-b-PFS26 (block ratio 1.0:22.5:1.0), was prepared through a combination of living anionic polymerization and end-to-end coupling. The block ratio and dispersity were established by a combination of MALDI-TOF mass spectrometry, 1H NMR, and GPC. Individual 1D fiber-like micelles with looped PDMS coronas were formed in mixed solvents of hexane and decane. Low length-dispersity fiber-like micelles of controlled length were prepared from short seed micelles of PFS26-b-PDMS584-b-PFS26 derived from sonication using the seeded growth method termed living crystallization-driven self-assembly. In addition, seeded growth of blends of both PFS26-b-PDMS584-b-PFS26 and PFS26 homopolymer and of PFS26-b-PDMS584-b-PFS26 and the analogous diblock copolymer PFS26-b-PDMS292 were also explored. Large aggregates with fiber-like protrusions were formed by spontaneous nucleation of the blends of PFS26-b-PDMS584-b-PFS26 and PFS26. High-aspect ratio ribbon-like micelles were formed by adding the blends of PFS26-b-PDMS584-b-PFS26 and PFS26 to the cylindrical PFS26-b-PDMS584-b-PFS26 seeds. In contrast, surprisingly, seeded growth of blends of PFS26-b-PDMS584-b-PFS26 and PFS26-b-PDMS292 or the individual components using seeds of either PFS26-b-PDMS584-b-PFS26 or PFS26-b-PDMS292 showed that growth was only detected in the case of matching of the seed and multiblock copolymer chemistries.

Original languageEnglish
Pages (from-to)3973-3982
Number of pages10
JournalPolymer Chemistry
Volume10
Issue number29
Early online date30 May 2019
DOIs
Publication statusPublished - 7 Aug 2019

Structured keywords

  • BCS and TECS CDTs

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