Synthesis and Self-Assembly of Diblock Copolymers through Hydrogen Bonding. Semiquantitative Determination of Binding Constants

Pan, Jing; Chen, Mingfei; Warner, William N.; He, Mingqian; Dalton, Larry R.; Hogen‐Esch, Thieo E.

doi:10.1021/ma000833+

Cited by 21 publications

(17 citation statements)

References 28 publications

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“…Pan et al used a similar strategy for the anionic synthesis of their PHEMA-b-PMMA diblock copolymers. 57 Their molecular weight of the block copolymer (4200 g/mol) and the PHEMA (400 g/mol), however, was small compared to our PHEMA segment, which possesses an average degree of polymerization of about 106 repeating units corresponding to a molecular weight of about 13.8 kg/mol. As seen from the comparison of the block copolymers 1c and 2c, the stoichiometry in the polymerizations was adjusted to result in similar ratio of A to B repeating units for 1c and 2c but significantly different total molecular weights.…”

Section: Synthesis and Characterization Of Azobenzene-functionalized mentioning

confidence: 69%

Blends of Poly(methacrylate) Block Copolymers with Photoaddressable Segments

et al. 2007

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The paper presents the synthesis of azobenzene-functionalized block copolymers based on a poly-(methyl methacrylate) (PMMA) segment and an azobenzene-functionalized poly(hydroxyethyl methacrylate) segment, and a basic study of blending these block copolymers with homopolymers is given. Two diblock copolymers, prepared via different routes, were synthesized by a living anionic polymerization followed by a polymer analogous reaction to attach the azobenzene side groups. Self-assembly of the block copolymers resulted in phase-separated morphologies on the nanometer scale. The photoaddressable azobenzene segments are dispersed in the PMMA matrix and locally confined. Special focus is given to the preparation and characterization of block copolymer blends with PMMA homopolymer in order to dilute the phase-separated azobenzene morphology and reduce the optical density while maintaining the confinement. The block copolymer blends were characterized with respect to their morphology and initial holographic experiments were performed.

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Section: Synthesis and Characterization Of Azobenzene-functionalized mentioning

confidence: 69%

Blends of Poly(methacrylate) Block Copolymers with Photoaddressable Segments

et al. 2007

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“…This includes a regular lamellar structure for the block copolymer and another in-lamella periodicity, whose stacking direction is perpendicular to the regular lamellar array. Hogen-Esch et al investigated the structure of a diblock copolymer/diblock copolymer blend that included a hydrogen bonding interaction and observed a three phase structure, 51 while Jiang et al observed hierarchical structures from a triblock terpolymer/diblock copolymer system, styrene-block-butadiene-block-tert-butylmethacrylate(SBT)/styrene-block-2-vinylpyridine, 52 where poly(tert-butylmethacrylate) was partially saponificated.…”

Section: 50mentioning

confidence: 99%

Precise Molecular Design of Complex Polymers and Morphology Control of Their Hierarchical Multiphase Structures

Matsushita

2008

Polym J

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This report reviews the recent advances in morphological studies on block copolymer and related multiple component polymer systems that possess characteristic chain connectivity and non-covalent bonding interactions, which were mostly done in our research group. Among many topics, three types of multi-phase systems are picked up and examined in this article. The first system consists of multiblock terpolymers. Hierarchical structures having double periodicity have been formulated for sample polymers including block chains with different lengths. The second one is represented by star-shaped terpolymers of the ABC type, which easily form three-phase cylinder-like structure whose cross sections exhibit periodic tiling structures. They show several Archimedean tilings and one of them forms quasicrystalline tiling with dodecagonal symmetry. The third one is composed of block copolymer/block copolymer blends or a block copolymer/homopolymer blend with hydrogen bonding interactions. It has been found these blends represent very striking phase structures including new mesoscopic tiling structures. These structures with new self-assembly manners due to strategic molecular design open the door to production of many highly functional materials.KEY WORDS: Block Polymer / Morphology / Hierarchical Structure / Archimedean Tiling / Quasicrystalline Tiling / Studies on self-assembling structures of block copolymers have started in the 1960s, when the first reports on the discovery of highly periodic structures for block copolymers in bulk and in concentrated solutions were published.1,2 Successively, these structures were verified by measurements of viscoelastic and thermal properties 3,4 and finally observed by morphological studies with electron microscopy. 5,6 The basic concept of morphological transition with composition was proposed during this period, 7 since then the concept has been the basis of any morphological studies in block copolymerbased complex systems. Subsequently, started from the 1970s through the early 1990s, morphological features were extensively studied both by theoretical 8-10 and experimental works.11-13 During this period, physical aspects of several properties such as phase transition and phase stability were fully focused, where the order-order phase transition 9,14 or order-disorder transition 9,15 was investigated by varying the magnitudes of the external field such as shear flow and/or temperature. Moreover, nanophase-separated structures were explored at the molecular level using neutron scattering methods by introducing deuterium labeling technique in this period. 16,17 The next generation occurred during the late 1980s and 1990s when complex morphologies with periodic surfaces were identified, some of which included bicontinuous structures for two-component linear 18 and star-branched 19 copolymers, as well as tricontinuous structures for three-component linear terpolymers. 20 The peculiar morphology for an amphiphilic diblock copolymer-aluminosilicate nanocomposite was also reported. 21 Among...

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“…We hypothesized that this system would exhibit a more complex behavior compared to classical systems because of the additional functionality of the P(HEMA-co-PEMA) block. Besides the hydrogenbonding capability that is characteristic of PHEMA, 15 this statistical segment also features ionizable units by virtue of a neutralization reaction involving phosphonic diacid moieties of PHEMA.…”

Section: Introductionmentioning

confidence: 99%

Nanostructure of polystyrene-b-poly(2-hydroxyethyl methacrylate) and derivatives with phosphonic diacid groups

Schmidt

Giacomelli

2012

J. Braz. Chem. Soc.

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A engenharia de superfícies para o posicionamento de biomoléculas é uma etapa fundamental para a produção de biochips. Neste estudo, descreve-se uma nova estratégia para a preparação de nanodomínios contendo grupos ácido fosfônicos, os quais se ligam a uma família de proteínas (anexinas), de forma reversível em função da presença de íons cálcio. A abordagem desenvolvida consistiu no uso de precursores de poliestireno-b-poli(metacrilato de 2-hidroxietila) (PS-b-PHEMA) sintetizados por polimerização radicalar por transferência de átomos (ATRP) para a obtenção de cilindros de PS (f PS = 0.25-0.27) dispostos em morfologia hexagonal numa matriz de PHEMA. Os grupos hidroxila pendentes do PHEMA foram, em seguida, parcialmente (20%) convertidos em grupos ácido fosfônicos por reações sequenciais de fosforilação, sililação e metanólise. Este processo produziu derivados PS-b-P(HEMA-co-PEMA) que retêm a morfologia hexagonal, embora o grau de organização estrutural seja menor em relação aos precursores.Surface engineering for precise positioning of biomolecules is of particular interest for controlled fabrication of biochips. In this study, a novel approach for the preparation of nanodomains with phosphonic diacid groups that were previously shown to reversibly bind to a family of proteins (annexins) in a calcium-dependent manner is described. The strategy makes use of polystyreneb-poly(2-hydroxyethyl methacrylate) (PS-b-PHEMA) precursors prepared by atom transfer radical polymerization (ATRP) to obtain hexagonally packed PS cylinders (f PS = 0.25-0.27) in a PHEMA matrix. The pendant hydroxyl groups of PHEMA are then partially (ca. 20%) converted into phosphonic diacid groups via sequential reactions involving phosphorylation, silylation and methanolysis. This process produces PS-b-P(HEMA-co-PEMA) derivatives that still retain the hexagonal morphology, but their degree of structural organization is reduced comparatively to the precursors.

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Synthesis and Self-Assembly of Diblock Copolymers through Hydrogen Bonding. Semiquantitative Determination of Binding Constants

Cited by 21 publications

References 28 publications

Blends of Poly(methacrylate) Block Copolymers with Photoaddressable Segments

Blends of Poly(methacrylate) Block Copolymers with Photoaddressable Segments

Precise Molecular Design of Complex Polymers and Morphology Control of Their Hierarchical Multiphase Structures

Nanostructure of polystyrene-b-poly(2-hydroxyethyl methacrylate) and derivatives with phosphonic diacid groups

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