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Poly(Vinylformamide- co -Vinylamine)/Inorganic Oxide Hybrid Materials

  • Chapter
Polyelectrolytes with Defined Molecular Architecture I

Part of the book series: Advances in Polymer Science ((POLYMER,volume 165))

Abstract

Novel ways to synthesize poly(vinylamine)/silica hybrid materials rich in free amino moieties using vinylformamide (VFA) as the key monomer are reported. Such materials are accessible from poly(vinylamine) which is obtained from radically produced poly(vinylformamide) (PVFA) which was either immobilized on to silica surfaces from solution and converted into poly(vinylamine- co -vinylformamide) polymers (PVFA- co -PVAm) by acidic hydrolysis, or by acidic hydrolysis in solution with subsequent adsorption on to silica. We adsorbed control PVFA- co -PVAm samples of different molecular masses and co-polymer compositions from aqueous solutions on to inorganic surfaces such as silica or titania simply by pH control. Direct surface functionalization using the VFA monomers was possible by their radical graft co-polymerization with bifunctional monomers, for example 1,3-divinylimidazolid-2-one (BVU) or on silica particles which were pre-functionalized with vinyltriethoxysilane (VTS). The influence of the amino content and molar mass (4000, 40,000, and 400,000 g mol−1) of PVFA- co -PVAm on the degree of surface coverage, charging, and polarity was studied using X-ray photoelectron spectroscopy (XPS), potentiometric titrations, and electrokinetic measurements, and solvatochromic probes. It was shown that the amino content of the co-polymer has a significant influence on the amount of polymer adsorbed, the layer thickness, and surface polarity. Post-functionalization reactions with isocyanates or fullerene were used as a suitable method for enhancing the stability of the polyelectrolyte layer on the inorganic surface. They also open the way to producing multi-functional hybrid materials. The adsorption and post-functionalization of PVFA- co -PVAm samples on to gold-coated silicon wafer surfaces was used to build up laterally patterned surfaces for sensors and biological applications.

In memory of Professor Dr Hans-Jörg Jacobasch and to honor his work in surface sciences

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Abbreviations

ABAC:

2,2′-Azobis-(2-amidinopropene) dihydrochloride

AFM:

Atomic force microscopy

βb:

Surface basicity parameter

BICDPM:

4,4′-(Bisisocyanate)diphenyl methane

BVU:

1,3-Divinylimidazolid-2-one

CP:

Cross polarization

EPR:

Electron paramagnetic resonance

IEP:

Isoelectric point (IEP=pH|ξx=0)

HBD:

Hydrogen bond donating

MAS:

Magic angle spinning

n :

Number of correlation points

PBVH:

Poly(1,3-divinylimidazolid-2-one)

PVFA:

Poly(vinylformamide)

PVFA- co -PBVH:

Poly(vinylformamide- co -1,3-divinylimidazolid-2-one)

PVFA- co -PVAm:

Poly(vinylformamide- co -vinylamine)

PVAm- co -PBVH:

Poly(vinylamine- co -1,3-divinylimidazolid-2-one)

PVFA- co -PVAm-x:

Poly(vinylformamide- co -vinylamine) which contains x w/w-% of the PVAm fraction (randomly distributed)

PVAm:

Poly(vinylformamine)

r :

Correlation coefficient

σ :

Standard deviation

SAM:

Self-assembled monolayer

SANS:

Small angle neutron scattering

VFA:

Vinylformamide

VTS:

Vinyltriethoxysilane

VTS-silica:

Vinyltriethoxysilane grafted on to silica

ξ :

Correlation length

XPS:

X-ray photoelectron spectroscopy

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Acknowledgement

The generous financial support of this project by the Deutsche Forschungsgemeinschaft (DFG), BASF AG Ludwigshafen, and the Fonds der Chemischen Industrie is gratefully acknowledged.

We thank the following scientists for co-operation (see also the Refs. [60, 65, 69, 99]): solid-state NMR spectroscopy was performed by Dipl.-Phys. Stephanie Hesse and Professor Christian Jäger (Institute of Physics, Friedrich Schiller University Jena) and Dr Hartmut Komber (Institute of Polymer Research, Dresden); the EPR spectra were measured by Dr Manfred Friedrich (Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University Jena), electrokinetic measurements were carried out by Dr Cornelia Bellmann (Institute of Polymer Research, Dresden), and SANS measurements performed in Grenoble were supported by Dr Thomas Hellweg (Iwan N. Stranski Institute, Berlin).

Furthermore, we thank Professor Christian Reichardt (University of Marburg) for generously providing betaine dyes 1 and 2, and Dr Gunnar Schornick and Dr Rainer Dyllick-Brenzinger (BASF AG, Ludwigshafen) for providing chemicals and discussions.

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Author notes

  1. Ina Voigt

    Present address: Institute of Polymer Research, Hohe Strasse 6, 01069, Dresden, Germany

  2. Katrin Estel

    Present address: Semiconductor and Microsystems Technology Laboratory, Dresden University of Technology, 01062, Dresden, Germany

Authors and Affiliations

  1. Department of Polymer Chemistry, Chemnitz University of Technology, Strasse der Nationen 62, 09111Chemnitz, Germany

    Stefan Spange, Torsten Meyer & Ina Voigt

  2. Institute of Polymer Research, Hohe Strasse 6, 01069, Dresden, Germany

    Michael Eschner, Katrin Estel, Dieter Pleul & Frank Simon

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  1. Stefan Spange
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Correspondence to Stefan Spange .

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Spange, S. et al. (2004). Poly(Vinylformamide- co -Vinylamine)/Inorganic Oxide Hybrid Materials. In: Schmidt, M. (eds) Polyelectrolytes with Defined Molecular Architecture I. Advances in Polymer Science, vol 165. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b11267

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  • DOI: https://doi.org/10.1007/b11267

  • Publisher Name: Springer, Berlin, Heidelberg

  • Print ISBN: 978-3-540-00528-5

  • Online ISBN: 978-3-540-36433-7

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