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Issue 29, 2019
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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

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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.

Graphical abstract: 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

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Supplementary files

Article information


Submitted
13 Mar 2019
Accepted
29 May 2019
First published
30 May 2019

Polym. Chem., 2019,10, 3973-3982
Article type
Paper

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

Q. Zhang, Y. He, A. M. Oliver, S. Pearce, R. L. Harniman, G. R. Whittell, Y. Liu, S. Du, J. Leng and I. Manners, Polym. Chem., 2019, 10, 3973
DOI: 10.1039/C9PY00401G

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