Microphase separation under constraints: a molecular thermodynamic theory for polyelectrolytic amphiphilic model networks in water

Georgiou, Theoni K.; Vamvakaki, Maria; Patrickios, Costas S.

doi:10.1016/j.polymer.2004.08.024

Cited by 51 publications

(46 citation statements)

References 50 publications

(74 reference statements)

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“…For shorter I blocks, and above a certain concentration dendronlike micellar aggregates can be formed due to a loop to bridge transition and finally a three-dimensional physical network structure is obtained. A molecular thermodynamic theory, which considers various possible morphologies of the networks (spherical, cylindrical, lamellar and unimers) has been developed by Georgiou et al [22]. If an insoluble block is replaced by a soluble block, a completely different kind of micelles are formed.…”

Section: Self-assembly Of Triblock Copolymersmentioning

confidence: 99%

Assembly of polyelectrolyte-containing block copolymers in aqueous media

Stuart

Hofs

Voets

et al. 2005

Current Opinion in Colloid & Interface Science

148

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Section: Self-assembly Of Triblock Copolymersmentioning

confidence: 99%

Assembly of polyelectrolyte-containing block copolymers in aqueous media

Stuart

Hofs

Voets

et al. 2005

Current Opinion in Colloid & Interface Science

148

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“…The synthesis of conetworks composed of polymer chains of well‐defined molecular weight (MW) and composition19 requires the use of controlled polymerization techniques 20. To this end, for the past 9 years our research team has been employing such controlled methods for the preparation of APCNs of improved structure by sequential polymerization and end‐linking in one pot 21–28…”

Section: Introductionmentioning

confidence: 99%

Anionic amphiphilic end‐linked conetworks by the combination of quasiliving carbocationic and group transfer polymerizations

Kali

Georgiou

Iván

et al. 2009

J. Polym. Sci. A Polym. Chem.

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A series of amphiphilic end-linked conetworks was synthesized by the combination of two ''quasiliving'' polymerization techniques, quasiliving carbocationic (QLCCP) and group transfer polymerizations (GTP). The hydrophobic monomer was polyisobutylene methacrylate synthesized by the QLCCP of isobutylene and subsequent terminal modification reactions. The hydrophilic monomer was methacrylic acid (MAA) introduced via the polymerization of 2-tetrahydropyranyl methacrylate followed by acid hydrolysis after (co)network formation. The conetwork syntheses were performed by sequential monomer/crosslinker additions under GTP conditions. All the precursors and the extractables from the conetworks were characterized by gel permeation chromatography and 1 H NMR. The resulting polymer conetworks were investigated in terms of their degree of swelling (DS) in aqueous media and in tetrahydrofuran (THF) over the whole range of ionization of the MAA units and in nhexane for uncharged conetworks. The DSs in water increased with the degree of ionization (DI) of the MAA units and the hydrophilic content in the conetwork, whereas the DSs in THF increased with the reduction of the DI of the MAA units. The effective pK of the MAA units in the conetworks increased from 8.4 to 10.5 with decreasing MAA content. These findings can facilitate the design of similar unique conetworks with adjustable swelling behavior and composition-dependent pK values.

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“…More specifically, we will consider a regular network of endlinked diblock copolymers. Experimentally, the synthesis of such ideal copolymer networks is coming within reach [43], and simple phenomenological theories have been devised to predict the expected microphase separation [44,45]. A more refined SCF theory which can predict the phase behavior of such systems based on molecular parameters is thus clearly desirable.…”

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confidence: 99%

Self-Consistent Field Approach for Cross-Linked Copolymer Materials

Schmid

2013

Phys. Rev. Lett.

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A generalized self-consistent field approach for polymer networks with fixed topology is developed. It is shown that the theory reproduces the localization of crosslinks which is characteristic for gels. The theory is then used to study the order-disorder transition in regular networks of endlinked diblock copolymers. Compared to diblock copolymer melts, the transition is shifted towards lower values of the incompatibility parameter χ (the Flory-Huggins parameter). Moreover, the transition becomes strongly first order already at the mean-field level. If stress is applied, the transition is further shifted and finally vanishes in a critical point.PACS numbers: 64.70. Nd, 64.75.Nd, 6.25.hp, 47.57.jb Polymers are macromolecules made of a large number of structurally identical or similar subunits (monomers), with local monomer interactions that tend to be weak on the scale of the thermal energy k B T . In polymeric materials, molecules typically have many interaction partners. Therefore, these systems can often be described quite satisfactorily by mean field theories. In particular, the self-consistent field (SCF) theory [1-6] is a powerful mean field approach for describing inhomogeneous polymer melts and solutions. Originally developed as a theory for interfaces between immiscible homopolymer phases [1], it has by now become a standard tool for studying phase transitions between block copolymer mesophases [7][8][9], the self-organization of amphiphilic polymers in solution [10], or the structure of polymer composite materials [11][12][13], to name just a few examples. Numerous extensions have been proposed that allow one to include, e.g., orientational order [14], electrostatic interactions [15], dynamical processes [16][17][18][19] or the effect of fluctuations [20][21][22].Despite these successes, the SCF theory still suffers from severe restrictions. Most prominently, it is limited to fluids. Polymers are taken to have full translational freedom and, consequently, the systems cannot sustain large shear stress or elastic deformations. Complex fluids may respond elastically to small stress to some extent, and this can be studied by SCF methods [23,24], but they necessarily yield to large stress. In reality, however, many materials of interest such as rubber are irreversibly crosslinked, either chemically or physically. Crosslinking is a popular strategy for stabilizing composite materials or polymeric nanostructures. While SCF approaches have been devised for describing systems of reversibly crosslinked polymeric materials [25][26][27], there exists so far no SCF theory for irreversibly crosslinked polymer networks.In the present paper, we propose a way to overcome this limitation. We develop a SCF approach for irreversibly crosslinked networks with fixed (quenched) topology.As an application example, we then use the method to study the phase behavior of symmetric cross-linked diblock copolymers. Specifically, we address the question how crosslinking affects the order-disorder transition (ODT), i.e., the trans...

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Microphase separation under constraints: a molecular thermodynamic theory for polyelectrolytic amphiphilic model networks in water

Cited by 51 publications

References 50 publications

Assembly of polyelectrolyte-containing block copolymers in aqueous media

Assembly of polyelectrolyte-containing block copolymers in aqueous media

Anionic amphiphilic end‐linked conetworks by the combination of quasiliving carbocationic and group transfer polymerizations

Self-Consistent Field Approach for Cross-Linked Copolymer Materials

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