Hyper-cross-linked, hybrid membranes via interfacial polymerization

Michiel Raaijmakers

Research output: ThesisPhD Thesis - Research UT, graduation UT

289 Downloads (Pure)

Abstract

Hyper-cross-linked, hybrid membranes consist of covalent networks of alternating organic and inorganic, or biological groups. This thesis reports on the preparation of such hybrid networks via interfacial polymerization. The structure-property relationships of the hybrid networks depend strongly on the type, size and flexibility of the constituents. The collection of polymers that can be synthesized via interfacial polymerization includes polyamides, polyurethanes, polyureas, polyanilines, polyimides, and polycarbonates. In addition, the technique can be used to prepare defect-free, ultrathin films of metal organic frameworks, organic-inorganic hybrids, and bio-hybrids. Here, inorganic-organic network materials based on polyhedral oligomeric silsesquioxanes (POSS) that are covalently bound by imide bridges have been prepared. The membranes are characterized by a high degree of cross-linking, as a result of the large number of functional groups on the POSS cages. Even at temperatures up to 300 °C, macromolecular dynamics of the hybrid networks based on short imide bridges is limited. This is illustrated by the relatively small shrinkage during heat treatment of the poly[POSS-(amic acid)] precursors and the high permselectivities in gas separation applications at a broad temperature range. Poly(POSS imide)s with long, flexible imide bridges display a higher degree of network flexibility. The flexibility of the hybrid network materials prepared with relatively long imide bridges is reflected by the unique sorption behavior of fluoroalkane based poly(POSS-imide). The membrane layers sorb large amounts of CO2 and CH4, up to an extent that the molar volume of the adsorbed gas exceeds that of the liquid molar volume of these gases. The interfacial polymerization method used for the inorganic-organic networks has been extended towards biological hybrids. The preparation of all-protein layers that consist of enzymatically active and fluorescently active films is reported. The broad applicability of interfacial polymerization for the preparation of ultrathin hybrid films provide prospect for further development of materials with unique functionalities.
Original languageEnglish
Awarding Institution
  • University of Twente
Supervisors/Advisors
  • Benes, N.E., Supervisor
  • Nijmeijer, A., Supervisor
Award date2 Oct 2015
Place of PublicationEnschede
Publisher
Print ISBNs978-90-365-3967-8
DOIs
Publication statusPublished - 2 Oct 2015

Fingerprint

Imides
Polymerization
Membranes
polycarbonate
Gases
Density (specific gravity)
Polyurethanes
Ultrathin films
Nylons
Polyimides
Functional groups
Sorption
Polymers
Metals
Heat treatment
Temperature
Defects
Acids
Liquids

Keywords

  • IR-97200
  • METIS-311740
  • EC Grant Agreement nr.: FP7/263007

Cite this

Raaijmakers, Michiel. / Hyper-cross-linked, hybrid membranes via interfacial polymerization. Enschede : Universiteit Twente, 2015. 292 p.
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abstract = "Hyper-cross-linked, hybrid membranes consist of covalent networks of alternating organic and inorganic, or biological groups. This thesis reports on the preparation of such hybrid networks via interfacial polymerization. The structure-property relationships of the hybrid networks depend strongly on the type, size and flexibility of the constituents. The collection of polymers that can be synthesized via interfacial polymerization includes polyamides, polyurethanes, polyureas, polyanilines, polyimides, and polycarbonates. In addition, the technique can be used to prepare defect-free, ultrathin films of metal organic frameworks, organic-inorganic hybrids, and bio-hybrids. Here, inorganic-organic network materials based on polyhedral oligomeric silsesquioxanes (POSS) that are covalently bound by imide bridges have been prepared. The membranes are characterized by a high degree of cross-linking, as a result of the large number of functional groups on the POSS cages. Even at temperatures up to 300 °C, macromolecular dynamics of the hybrid networks based on short imide bridges is limited. This is illustrated by the relatively small shrinkage during heat treatment of the poly[POSS-(amic acid)] precursors and the high permselectivities in gas separation applications at a broad temperature range. Poly(POSS imide)s with long, flexible imide bridges display a higher degree of network flexibility. The flexibility of the hybrid network materials prepared with relatively long imide bridges is reflected by the unique sorption behavior of fluoroalkane based poly(POSS-imide). The membrane layers sorb large amounts of CO2 and CH4, up to an extent that the molar volume of the adsorbed gas exceeds that of the liquid molar volume of these gases. The interfacial polymerization method used for the inorganic-organic networks has been extended towards biological hybrids. The preparation of all-protein layers that consist of enzymatically active and fluorescently active films is reported. The broad applicability of interfacial polymerization for the preparation of ultrathin hybrid films provide prospect for further development of materials with unique functionalities.",
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Hyper-cross-linked, hybrid membranes via interfacial polymerization. / Raaijmakers, Michiel.

Enschede : Universiteit Twente, 2015. 292 p.

Research output: ThesisPhD Thesis - Research UT, graduation UT

TY - THES

T1 - Hyper-cross-linked, hybrid membranes via interfacial polymerization

AU - Raaijmakers, Michiel

N1 - FP7/263007

PY - 2015/10/2

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N2 - Hyper-cross-linked, hybrid membranes consist of covalent networks of alternating organic and inorganic, or biological groups. This thesis reports on the preparation of such hybrid networks via interfacial polymerization. The structure-property relationships of the hybrid networks depend strongly on the type, size and flexibility of the constituents. The collection of polymers that can be synthesized via interfacial polymerization includes polyamides, polyurethanes, polyureas, polyanilines, polyimides, and polycarbonates. In addition, the technique can be used to prepare defect-free, ultrathin films of metal organic frameworks, organic-inorganic hybrids, and bio-hybrids. Here, inorganic-organic network materials based on polyhedral oligomeric silsesquioxanes (POSS) that are covalently bound by imide bridges have been prepared. The membranes are characterized by a high degree of cross-linking, as a result of the large number of functional groups on the POSS cages. Even at temperatures up to 300 °C, macromolecular dynamics of the hybrid networks based on short imide bridges is limited. This is illustrated by the relatively small shrinkage during heat treatment of the poly[POSS-(amic acid)] precursors and the high permselectivities in gas separation applications at a broad temperature range. Poly(POSS imide)s with long, flexible imide bridges display a higher degree of network flexibility. The flexibility of the hybrid network materials prepared with relatively long imide bridges is reflected by the unique sorption behavior of fluoroalkane based poly(POSS-imide). The membrane layers sorb large amounts of CO2 and CH4, up to an extent that the molar volume of the adsorbed gas exceeds that of the liquid molar volume of these gases. The interfacial polymerization method used for the inorganic-organic networks has been extended towards biological hybrids. The preparation of all-protein layers that consist of enzymatically active and fluorescently active films is reported. The broad applicability of interfacial polymerization for the preparation of ultrathin hybrid films provide prospect for further development of materials with unique functionalities.

AB - Hyper-cross-linked, hybrid membranes consist of covalent networks of alternating organic and inorganic, or biological groups. This thesis reports on the preparation of such hybrid networks via interfacial polymerization. The structure-property relationships of the hybrid networks depend strongly on the type, size and flexibility of the constituents. The collection of polymers that can be synthesized via interfacial polymerization includes polyamides, polyurethanes, polyureas, polyanilines, polyimides, and polycarbonates. In addition, the technique can be used to prepare defect-free, ultrathin films of metal organic frameworks, organic-inorganic hybrids, and bio-hybrids. Here, inorganic-organic network materials based on polyhedral oligomeric silsesquioxanes (POSS) that are covalently bound by imide bridges have been prepared. The membranes are characterized by a high degree of cross-linking, as a result of the large number of functional groups on the POSS cages. Even at temperatures up to 300 °C, macromolecular dynamics of the hybrid networks based on short imide bridges is limited. This is illustrated by the relatively small shrinkage during heat treatment of the poly[POSS-(amic acid)] precursors and the high permselectivities in gas separation applications at a broad temperature range. Poly(POSS imide)s with long, flexible imide bridges display a higher degree of network flexibility. The flexibility of the hybrid network materials prepared with relatively long imide bridges is reflected by the unique sorption behavior of fluoroalkane based poly(POSS-imide). The membrane layers sorb large amounts of CO2 and CH4, up to an extent that the molar volume of the adsorbed gas exceeds that of the liquid molar volume of these gases. The interfacial polymerization method used for the inorganic-organic networks has been extended towards biological hybrids. The preparation of all-protein layers that consist of enzymatically active and fluorescently active films is reported. The broad applicability of interfacial polymerization for the preparation of ultrathin hybrid films provide prospect for further development of materials with unique functionalities.

KW - IR-97200

KW - METIS-311740

KW - EC Grant Agreement nr.: FP7/263007

U2 - 10.3990/1.9789036539678

DO - 10.3990/1.9789036539678

M3 - PhD Thesis - Research UT, graduation UT

SN - 978-90-365-3967-8

PB - Universiteit Twente

CY - Enschede

ER -