Amphiphiles coordinated to block copolymer as a template for mesoporous materials

Sami Valkama; Teemu Ruotsalainen; Harri Kosonen; Janne Ruokolainen; Mika Torkkeli; Ritva Serimaa; Gerrit ten Brinke; Olli Ikkala

doi:10.1021/ma020538k

Amphiphiles coordinated to block copolymer as a template for mesoporous materials

Sami Valkama, Teemu Ruotsalainen, Harri Kosonen, Janne Ruokolainen, Mika Torkkeli, Ritva Serimaa, Gerrit ten Brinke (Corresponding Author), Olli Ikkala (Corresponding Author)

VTT Technical Research Centre of Finland

Research output: Contribution to journal › Article › Scientific › peer-review

55 Citations (Scopus)

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 wide-angle 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.

Original language	English
Pages (from-to)	3986-3991
Journal	Macromolecules
Volume	36
Issue number	11
DOIs	https://doi.org/10.1021/ma020538k
Publication status	Published - 2003
MoE publication type	A1 Journal article-refereed

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@article{e3a5afca6d3e4b19b69b117e4a386b4e,

title = "Amphiphiles coordinated to block copolymer 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 wide-angle 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.",

author = "Sami Valkama and Teemu Ruotsalainen and Harri Kosonen and Janne Ruokolainen and Mika Torkkeli and Ritva Serimaa and Brinke, {Gerrit ten} and Olli Ikkala",

year = "2003",

doi = "10.1021/ma020538k",

language = "English",

volume = "36",

pages = "3986--3991",

journal = "Macromolecules",

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publisher = "American Chemical Society ACS",

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T1 - Amphiphiles coordinated to block copolymer as a template for mesoporous materials

AU - Valkama, Sami

AU - Ruotsalainen, Teemu

AU - Kosonen, Harri

AU - Ruokolainen, Janne

AU - Torkkeli, Mika

AU - Serimaa, Ritva

AU - Brinke, Gerrit ten

AU - Ikkala, Olli

PY - 2003

Y1 - 2003

N2 - 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 wide-angle 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.

AB - 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 wide-angle 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.

U2 - 10.1021/ma020538k

DO - 10.1021/ma020538k

M3 - Article

SN - 0024-9297

VL - 36

SP - 3986

EP - 3991

JO - Macromolecules

JF - Macromolecules

IS - 11

ER -

Amphiphiles coordinated to block copolymer as a template for mesoporous materials

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