Microphase Separation of Cyclic Block Copolymers of Styrene and Butadiene and of Their Corresponding Linear Triblock Copolymers

Zhu, Yuqing; Gido, Samuel P.; Iatrou, Hermis; Hadjichristidis, Nikos; Mays, Jimmy W.

doi:10.1021/ma021408e

Cited by 73 publications

(73 citation statements)

References 14 publications

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“…[1][2][3][4][5][6][7][8][9][10] In addition, cyclic block copolymers have received interest due to selfassembly characteristics that deviate from the typical behaviours of their linear analogues. 3,5,[11][12][13][14][15][16][17][18][19][20][21][22][23][24] In the case of micelle formation in solution, cyclic block copolymers were reported to form relatively more compact micelles than their linear analogues. [11][12][13]15,16,18,23 The cyclic block copolymer micelles, however, were very often evaluated qualitatively.…”

Section: Introductionmentioning

confidence: 99%

Well-defined and stable nanomicelles self-assembled from brush cyclic and tadpole copolymer amphiphiles: a versatile smart carrier platform

et al. 2017

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This study reports the first well-defined and stable nanomicelles (20 − 30 nm in diameter) self-assembled from amphiphilic brush (comb-like) cyclic and tadpole-shaped copolymers composed of hydrophobic n-decyl and hydrophilic 2-(2-methoxyethoxy)ethoxy) ethyl bristle blocks based on a poly(glycidyl ether) backbone. The micelle formation behaviour and structural details were investigated by synchrotron X-ray scattering analysis in a rigorous and complementary manner. The amphiphilic brush cyclic topology facilitates more compact and stable aggregation behaviour in the micelle core and a more densely packed corona, which prevents intermicellar aggregation. The presence of a hydrophobic component with brush cyclic topology inside the core is identified as the primary micelle stabilizing factor, enabling stable core aggregation and sharper core-corona interface formation. The presence of a hydrophilic brush cyclic component in the corona is determined as the secondary micelle stabilizing factor, helping nullify the corona penetration by polymer chains from other micelles and ultimately prevent the intermicellar aggregation-mediated collapse of the micellar structure. Overall, the brush cyclic topology was confirmed to be beneficial for forming highly stable nanomicelles with an extremely narrow (pseudo-monodisperse) size distribution compared with conventional linear topology and tadpole topologies. All the results of this study provide a unique opportunity for designing advanced functional high-performance amphiphilic materials for nanomicelles that are unattainable by other conventional methods and broadening their applications in various fields, including drug delivery, biomedical imaging, foods, cosmetics, smart coatings, photonics and molecular electronics.

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Section: Introductionmentioning

confidence: 99%

Well-defined and stable nanomicelles self-assembled from brush cyclic and tadpole copolymer amphiphiles: a versatile smart carrier platform

et al. 2017

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“…In these materials, two or more homopolymer chains are covalently bonded at their chain ends, and the interplay between the molecular connectivity among the different block chains and repulsive segmental interactions gives rise to a wide variety of microphaseseparated morphologies with characteristic length scales of several tens of nanometers. [1][2][3][4] Control of the morphology in the films, including both the orientation and ordering of the copolymer microdomains, is essential for such applications. In general, the morphologies of thin copolymer films can be tuned by the molecular weight and composition of the diblock copolymer, the surface-block interactions, and the film thickness.…”

Section: Introductionmentioning

confidence: 99%

Morphology of poly(styrene‐block‐dimethylsiloxane) copolymer films

Zheng

Huang

et al. 2007

J of Applied Polymer Sci

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The morphologies of poly(styrene-block-dimethylsiloxane) (PS-b-PDMS) copolymer thin films were analyzed via atomic force microscopy and transition electron microscopy (TEM). The asymmetric copolymer thin films spin-cast from toluene onto mica presented meshlike structures, which were different from the spherical structures from TEM measurements. The annealing temperature affected the surface morphology of the PS-b-PDMS copolymer thin films; the polydimethylsiloxane (PDMS) phases at the surface were increased when the annealing temperature was higher than the PDMS glass-transition temperature. The morphologies of the PS-b-PDMS copolymer thin films were different from solvent to solvent; for thin films spin-cast from toluene, the polystyrene (PS) phase appeared as pits in the PDMS matrix, whereas the thin films spin-cast from cyclohexane solutions exhibited an islandlike structure and small, separated PS phases as protrusions over the macroscopically flat surface. The microphase structure of the PS-b-PDMS copolymer thin films was also strongly influenced by the different substrates; for an asymmetric block copolymer thin film, the PDMS and PS phases on a silicon substrate presented a lamellar structure parallel to the surface at intervals.

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14] Besides a simple ring construction, [15] there exist three dicyclic polymer topologies, [16] that is, eight-shaped, [17] y-shaped, [18,19] and manacle-shaped [18,20] constructions. Attempts to realize such unusual polymer topologies are an ongoing challenge in synthetic polymer chemistry.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Polymeric Topological Isomers through Electrostatic Self‐Assembly and Covalent Fixation with Star Telechelic Precursors

Tezuka¹,

Tsuchitani²,

Oike³

2004

Macromol. Rapid Commun.

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Summary: A pair of macromolecular constitutional isomers having topologically distinctive, dicyclic constructions, that is, θ‐shaped and manacle‐shaped polymers, has been synthesized from a polymer self‐assembly, comprised of three‐armed star poly(tetrahydrofuran) [poly(THF)] having N‐phenylpyrrolidinium salt end groups carrying dicarboxylate counteranions (1S/2d). The presence of the two constitutional polymeric isomers was confirmed by means of a reversed‐phase liquid chromatography (RPC) technique. Moreover, size exclusion chromatography (SEC) showed that a major component possesses notably larger hydrodynamic volume than the others, and is assignable as a manacle‐shaped isomer while a minor component is assigned as a θ‐shaped isomer. The statistics of the covalent‐linking process of 1S/2d were consistent with the other experimental results.An “electrostatic self‐assembly and covalent fixation” process of a trifunctional star‐shaped precursor gives rise to θ‐shaped and manacle‐shaped polymers.imageAn “electrostatic self‐assembly and covalent fixation” process of a trifunctional star‐shaped precursor gives rise to θ‐shaped and manacle‐shaped polymers.

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Microphase Separation of Cyclic Block Copolymers of Styrene and Butadiene and of Their Corresponding Linear Triblock Copolymers

Cited by 73 publications

References 14 publications

Well-defined and stable nanomicelles self-assembled from brush cyclic and tadpole copolymer amphiphiles: a versatile smart carrier platform

Well-defined and stable nanomicelles self-assembled from brush cyclic and tadpole copolymer amphiphiles: a versatile smart carrier platform

Morphology of poly(styrene‐block‐dimethylsiloxane) copolymer films

Synthesis of Polymeric Topological Isomers through Electrostatic Self‐Assembly and Covalent Fixation with Star Telechelic Precursors

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