How a Small Modification of the Corona-Forming Block Redirects the Self-Assembly of Crystalline–Coil Block Copolymers in Solution

González‐Álvarez, María José; Jia, Lin; Guerin, Gérald; Ks, Kim; Du, Van An; Walker, Gilbert C.; Manners, Ian; Winnik, Mitchell A.

doi:10.1021/acs.macromol.6b01616

Cited by 17 publications

(19 citation statements)

References 62 publications

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“…Based on previous work from our laboratory, we knew that even small extents of quaternization of PFS-b-P2VP significantly affected the morphology of the micelles. 56 Here we limited the extent of methylation of the pyridine groups to 1 mol % to ensure the solubility of the quaternized unimer PFS35-b-P2VP400 Q in THF (see NMR in Figure S9). This corresponds to an average of about four 2VP Q units per BCP chain.…”

Section: Decreasing the Growth Rate Of Pfs-b-p2vp By Quaternization (mentioning

confidence: 99%

Competitive Self-Assembly Kinetics as a Route To Control the Morphology of Core-Crystalline Cylindrical Micelles

Zhou

et al. 2018

J. Am. Chem. Soc.

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Nucleated self-assembly in selective solvents of core-crystalline block copolymers (BCPs) is a special case of living supramolecular polymerization, leading to rodlike micelles of controlled and uniform length. For the crystallization-driven self-assembly of PFS-containing BCPs (PFS = polyferrocenyldimethylsilane), the formation of block comicelles by sequential addition of different BCPs is well-established. But there are only a few examples of living copolymerization, the simultaneous addition of pairs of BCPs with different corona-forming chains. At present, relatively little is known about the competitive kinetics of different BCPs crystallizing on a common seed. Here we report a systematic study of the competitive seeded growth kinetics of pairs of linear PFS-containing BCPs and show that one can manipulate the kinetics to control the morphology of the comicelles. We found that the seeded-growth kinetics of the individual BCP unimer dominates the coassembly behavior and thus the morphology of the corona. Patchy comicelles with microphase-segregated corona chains are formed when the epitaxial growth rates of the two different BCPs on the common seed are similar. In contrast, factors that lead to dissimilar growth rates (long corona-forming blocks or introduction of charges on corona-forming chains) promote large-scale separation of the corona blocks, leading to block comicelles. Because the termini of the comicelles remain living, they can further direct the growth of unimers, resulting in hierarchical block comicelles with patchy blocks and single-component (homo) blocks. Furthermore, the patchy comicelles can be loaded with either gold or platinum nanoparticles, generating organic-inorganic hybrid materials with potential application in catalysis.

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Section: Decreasing the Growth Rate Of Pfs-b-p2vp By Quaternization (mentioning

confidence: 99%

Competitive Self-Assembly Kinetics as a Route To Control the Morphology of Core-Crystalline Cylindrical Micelles

Zhou

et al. 2018

J. Am. Chem. Soc.

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“…Since the w PEO was equal for all samples, the relative hydrophilicity of the corona block controlled the cylinder length. In another study, the corona size was manipulated using methyl iodide additive to quaternize poly(2‐vinyl pyridine) (P2VP) blocks of P2VP‐ b ‐PFS . The lightly quaternized (<6 mol%) P2VP forced the PFS to crystallize with slightly larger widths than unquaternized samples.…”

Section: Conventional Crystallizable Diblock Copolymersmentioning

confidence: 99%

“…This assembly was driven by the epitaxial attachment of the micelle PE core with the growth surface of the single crystal, similar to the report by Rizis and coworkers for PCL . and Gonzalez‐Alvarez et al .’s work with PFS . This hierarchical assembly was facilitated by the inclusion of homopolymer PE, which promoted the two different types of solution crystallization.…”

Section: Conventional Crystallizable Diblock Copolymersmentioning

confidence: 99%

“…In most cases, CDSA was used to form worm‐like micellar structures with crystalline cores of either PE or PFS . While the current focus of CDSA research is related to controlled micelle growth and hierarchical assembly, triblock terpolymers provide another opportunity to tailor the corona of the micelle to form “patchy” morphologies on the micelle surface . For diblock copolymers, this was achieved by mixing two copolymers .…”

Section: Conventional Crystallizable Triblock Copolymersmentioning

confidence: 99%

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Recent progress in block copolymer crystallization

Horn

Steffen

O'Connor

2018

Polymer Crystallization

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Block copolymers (BCPs) are important for technological advances in numerous industries, including but not limited to, electronics, biomedical, optics, environmental, and infrastructure. Because of their ubiquity, it is important to understand their hierarchical phase behavior to tune their macroscopic properties for efficient use. These macroscopic properties are derived from the microscopic self‐assembled structures. One unique form of hierarchical assembly exists when one or more of the polymeric blocks form lamellar crystals. These crystals are integral to understanding and predicting the macroscopic behavior. This review reports on recent advances in crystallization of BCPs, including bulk and solution assembly. Reports highlighting development in fundamental processes regarding crystallization mechanisms and behavior as well as for the design of practical applications are included.

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“…The solution self-assembly of PFS-block-polyelectrolyte materials is virtually unexplored and detailed studies are currently limited to materials in which the corona of PFSbased BCPs charge via the quaternisation of amino groups. [54][55][56] When 100% of the amino groups were quaternized, spherical micelles were formed in water. 54 However, in a separate study when between 1 and 3% of the corona was charged, platelet and scarf-like micelles formed.…”

Section: Introductionmentioning

confidence: 99%

Linear and Branched Fiber-like Micelles from the Crystallization-Driven Self-Assembly of Heterobimetallic Block Copolymer Polyelectrolyte/Surfactant Complexes

et al. 2019

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The solution self-assembly of a heterobimetallic diblock copolymer with a crystallisable poly(ferrocenyldimethylsilane) (PFS) core-forming block and a corona-forming segment featuring a poly(cobaltoceniumethylene) (PCE) based polyelectrolyte/surfactant complex, PFS50-b-[PCE][AOT]50 (AOT = bis(2-ethylhexyl) sulfosuccinate), has been explored. 2 Fiber-like micelles were formed in selective solvents for the Co block, presenting a corona in which every repeat unit bears a charge. We found that key features of the 1D morphologies were dependent on both the polarity of the solvent medium and temperature. In the most polar of the explored solvent media (iPrOH), seeded growth from 1D seeds of PFS50-b-P2VP739 (P2VP = poly(2-vinylpyridine)) yielded tapered B-A-B triblock co-micelles, where the width of the terminal B region derived from PFS-b-[PCE][AOT]n reduced on moving from the interface with the seed to the micelle termini. In addition, ca. 30 % of the micelles featured branching to yield multiple terminal blocks. On reducing the polarity of the solvent medium by the addition of 20% THF, the tapering of the micelles was no longer apparent, and the degree of branching was substantially increased to ca. 100 % of the population. With increased amounts of THF (30 %) the degree of branching reduced dramatically to ca. 3 %. In the least polar medium investigated (1:10 iPrOH:EtOAc), linear triblock co-micelles formed in which the terminal blocks were of consistent diameter, with no evidence for tapering or branching. However, significant unsymmetric growth (i.e. a higher degree of growth from one seed terminus compared to the other) to give noncentrosymmetric A-B diblock co-micelles was detected. Post self-assembly modification by coronal counterion exchange to alter the chemistry and solubility of the corona was also possible.

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How a Small Modification of the Corona-Forming Block Redirects the Self-Assembly of Crystalline–Coil Block Copolymers in Solution

Abstract: General rightsThis document is made available in accordance with publisher policies. Please cite only the published version using the reference above. ABSTRACTIn this study we examine how the self-assembly of crystalline-coil block copolymers in

Cited by 17 publications

References 62 publications

Competitive Self-Assembly Kinetics as a Route To Control the Morphology of Core-Crystalline Cylindrical Micelles

Competitive Self-Assembly Kinetics as a Route To Control the Morphology of Core-Crystalline Cylindrical Micelles

Recent progress in block copolymer crystallization

Linear and Branched Fiber-like Micelles from the Crystallization-Driven Self-Assembly of Heterobimetallic Block Copolymer Polyelectrolyte/Surfactant Complexes

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