Amphiphiles Coordinated to Block Copolymers as a Template for Mesoporous Materials

Abstract

We show a concept where coordination of amphiphiles to one block of a block copolymer leads to polymeric supramolecules and self-organization and that mesoporous materials can be achieved with a dense set of polymer brushes at the surfaces upon cleaving the amphiphiles by extraction with a selective solvent. Polystyrene-block-poly(4-vinylpyridine) (PS-block-P4VP) is used with zinc dodecylbenzenesulfonate (Zn(DBS) 2) which can coordinate to the lone electron pairs of the pyridine nitrogens in the P4VP block, leading to complexes PS-block-P4VP[Zn(DBS)2]y. Coordination of Zn(DBS)2 and structure formation were investigated using Fourier transformation infrared spectroscopy (FTIR), small-and wideangle X-ray scattering (SAXS and WAXS), and transmission electron microscopy (TEM). Lamellar structure was observed and even points toward a structural hierarchy for high molecular weight block copolymers. FTIR, SAXS, and TEM showed that most of Zn(DBS) 2 can be extracted from such templates using methanol, leading to lamellar porous structures. P4VP brushes cover the resulting pore surfaces. The structures do not collapse probably due to the glassy PS and defects in the nonaligned structure. Compared to hydrogen bonding, coordination allows bonding of higher molecular weight amphiphiles due to the stronger attraction.

From molecular modules to modular materials

“…(Fig. 4) [61]. The mesoporous material achieved with this complex shows a lamellar structure, and even points toward a structural hierarchy for high-molecular-weight block copolymer.…”

From molecular modules to modular materials

“…(Fig. 4) [61]. The mesoporous material achieved with this complex shows a lamellar structure, and even points toward a structural hierarchy for high-molecular-weight block copolymer.…”

Molecular Recognition in Structured Matrixes: Control of Guest Localization in Block Copolymer Films

“…The quantitative selectivity analysis afforded by the SIMS demonstrates the high fidelity of polymer functionalization that can be achieved through molecular recognition (as compared to polar interactions). Furthermore, it enables treating the complementary guests as building blocks that could be “plugged” into the polymer functionalities. , Taking advantage of our original design, where guest molecules differ substantially in volume, we set out to investigate our ability to control the equilibrium morphology of a recognition block copolymer by selectively swelling , the DAP-functionalized block using the dendritic guests.…”

Morphology of Rhenium Complex-Containing Polystyrene-block-poly(4-vinylpyridine) and Its Use as Self-Assembly Templates for Nanoparticles

“…This would generate a self-assembled structure whose pattern will be the replica of the P4VP(Re−DIAN) block. It was shown that PS−P4VP can be used as a template for mesoporous materials . The deposition of TiO 2 nanoparticles with a charged surface on polymers by the layer-by-layer deposition method has been used in the fabrication of solar cells …”

“…It was shown that PS-P4VP can be used as a template for mesoporous materials. 19 The deposition of TiO 2 nanoparticles with a charged surface on polymers by the layer-by-layer deposition method has been used in the fabrication of solar cells. 20 We have also demonstrated the use of the polyelectrolyte deposition method to fabricate solar cells using metalcontaining polymers.…”

From molecular modules to modular materials

“…(Fig. 4) [61]. The mesoporous material achieved with this complex shows a lamellar structure, and even points toward a structural hierarchy for high-molecular-weight block copolymer.…”

Molecular Recognition in Structured Matrixes: Control of Guest Localization in Block Copolymer Films

“…The quantitative selectivity analysis afforded by the SIMS demonstrates the high fidelity of polymer functionalization that can be achieved through molecular recognition (as compared to polar interactions). Furthermore, it enables treating the complementary guests as building blocks that could be “plugged” into the polymer functionalities. , Taking advantage of our original design, where guest molecules differ substantially in volume, we set out to investigate our ability to control the equilibrium morphology of a recognition block copolymer by selectively swelling , the DAP-functionalized block using the dendritic guests.…”

Morphology of Rhenium Complex-Containing Polystyrene-block-poly(4-vinylpyridine) and Its Use as Self-Assembly Templates for Nanoparticles

“…This would generate a self-assembled structure whose pattern will be the replica of the P4VP(Re−DIAN) block. It was shown that PS−P4VP can be used as a template for mesoporous materials . The deposition of TiO 2 nanoparticles with a charged surface on polymers by the layer-by-layer deposition method has been used in the fabrication of solar cells …”

“…It was shown that PS-P4VP can be used as a template for mesoporous materials. 19 The deposition of TiO 2 nanoparticles with a charged surface on polymers by the layer-by-layer deposition method has been used in the fabrication of solar cells. 20 We have also demonstrated the use of the polyelectrolyte deposition method to fabricate solar cells using metalcontaining polymers.…”

From molecular modules to modular materials

“…(Fig. 4) [61]. The mesoporous material achieved with this complex shows a lamellar structure, and even points toward a structural hierarchy for high-molecular-weight block copolymer.…”

Molecular Recognition in Structured Matrixes: Control of Guest Localization in Block Copolymer Films

“…The quantitative selectivity analysis afforded by the SIMS demonstrates the high fidelity of polymer functionalization that can be achieved through molecular recognition (as compared to polar interactions). Furthermore, it enables treating the complementary guests as building blocks that could be “plugged” into the polymer functionalities. , Taking advantage of our original design, where guest molecules differ substantially in volume, we set out to investigate our ability to control the equilibrium morphology of a recognition block copolymer by selectively swelling , the DAP-functionalized block using the dendritic guests.…”

Morphology of Rhenium Complex-Containing Polystyrene-block-poly(4-vinylpyridine) and Its Use as Self-Assembly Templates for Nanoparticles

“…This would generate a self-assembled structure whose pattern will be the replica of the P4VP(Re−DIAN) block. It was shown that PS−P4VP can be used as a template for mesoporous materials . The deposition of TiO 2 nanoparticles with a charged surface on polymers by the layer-by-layer deposition method has been used in the fabrication of solar cells …”

“…It was shown that PS-P4VP can be used as a template for mesoporous materials. 19 The deposition of TiO 2 nanoparticles with a charged surface on polymers by the layer-by-layer deposition method has been used in the fabrication of solar cells. 20 We have also demonstrated the use of the polyelectrolyte deposition method to fabricate solar cells using metalcontaining polymers.…”