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Nanostructures of Conducting Polymers

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Electrocatalytic Synthesis and Investigation of the Properties of Nanostructures on the Basis of Conducting Polymers Using Ionic Liquids as Ecologically Benign Electrolytes and Catalytic Media

Tech Area / Field

  • CHE-POL/Polymer Chemistry/Chemistry
  • CHE-SYN/Basic and Synthetic Chemistry/Chemistry
  • CHE-THE/Physical and Theoretical Chemistry/Chemistry

Status
3 Approved without Funding

Registration date
30.07.2003

Leading Institute
VNIIEF, Russia, N. Novgorod reg., Sarov

Supporting institutes

  • Moscow State University / Department of Chemistry, Russia, Moscow

Collaborators

  • Merck KGaA, Germany, Darmstadt\nH.C. Starck GmbH, Germany, Leverkusen\nUniversity of Minnesota / Chemical Engineering and Materials Science, USA, MN, Minneapolis\nSanta Fe Science and Technology, Inc., USA, NM, Santa Fe\nCNRS / Universite De Bourgogne, France, Dijon

Project summary

The project is devoted to the electrocatalytic synthesis and investigation of properties of nanostructures based on conducting polymers using ionic liquids as environmentally benign electrolytes and catalytic media. Development of the methods for synthesis of nanomaterials on the basis of conducting polymers, such as polyphenylenes, polythiophenes, polypyrroles, polyanilines and the like, including polyfullerenes is a challenging problem in view of ever growing interest to the nanostructured materials and their application in various areas.

Ionic liquids, i.e. room-temperature molten salts containing an organic cation, such as N-alkylheterocyclic moieties, and an inorganic anion, for instance, chlorometallates, fluoroborates or fluorophosphates, are nowadays considered as ecologically friendly solvents for various processes of organic synthesis. These non-toxic, non-volatile, and inflammable environmentally benign materials with controllable acid-base and hydrophilic-hydrophobic-oleophilic properties show promise in catalysis, including hydrocarbon conversion, electrocatalytic reactions, and polymer synthesis. The use of ionic liquids in these reactions will reduce the environmental risks and pollution.

The specific goals of this Project consist in the development of the methods for synthesis of the new types of ionic liquids based on various pyridinium, piperidinium, quinolinium, imidazolium and alkylammonium(phosphonium) salts with different anions, such as those derived from metal halides, sulfates and triflates and evaluation of the properties of ionic liquids in the following electrocatalytic reactions:

- Stereoregular oligomerization and polymerization of aromatic hydrocarbons, including benzene, biphenyl, terphenyl, naphthalene, alkylbenzenes using ionic liquids as electrolytic and catalytic media;

- Polymerization and polycondensation of heterocyclic monomers with the goal to prepare conducting polymers, such as polyanilines, polypyridines, polypyrroles, polythiophenes, polyimidazoles etc.;

- Electrocatalytic reactions of fullerenes in ionic liquids such as polycondensation or oligomerization of Buckminster fullerene or fluorinated fullerenes;

- Polymerization of functional aromatic compounds, inter alia benzenesulfonic acid or esters, biphenylsulfonic acid or esters etc.

The performance of ionic liquids in the title reactions will be rationalized on the basis of the structure and peculiar properties of ionic liquids. The relationship between the acid-base characteristics as well as electroconductivity and viscosity of ionic liquids, on the one hand, and their electrocatalytic properties, on the other hand, will be established.

This Project will stimulate the development of new environmentally benign solvents and catalysts for a variety of electrocatalytic syntheses of valuable organic products and polymers.

Recently, promising results were obtained in studying polymerization of some aromatic compounds in ionic liquids.

The following studies will be performed within this project:

(1) Study of the influence of the nature and structure of the cation and anion in the composition of the ionic liquid on the structure and properties of the conducting polymer prepared using this ionic liquid.

(2) Investigation of the effect of the main parameters of the electrocatalytic process (applied potential, nature of the electrode material, reaction temperature etc.) on the performance of ionic liquids in the polymerization processes.

(3) Comparison of the physicochemical properties of the conducting polymers prepared in ionic liquid and by the chemical methods.

(4) The systems (ionic liquids) listed below will be examined in relation to the effect of the acid-base and conducting properties of the ionic liquid on their catalytic properties in the polymerization of the above indicated substrates and on the physicochemical properties of the resulting polymers:

- Alkylammonium and imidazolium-based ionic liquids with chlorometalate, fluoroborate and fluorophosphate anions;
- Pyridinium, piperidinium and quinolinium-based ionic liquids with chlorometalate, fluoroborate and fluorophosphate anions;
- Binuclear (bridged) ionic liquids with different anions.


Among the methods of control of the state and properties of the conducting polymers, as well as ionic liquids and mechanisms of their electrocatalytic behaviour, the following methods and equipment available at the RFNC-VNIIEF and MSU will be used: FT-IR spectroscopy, EPR spectroscopy, X-ray photoelectron spectroscopy (XPS), electron microscopy, conductivity measurements, chemical analysis, scanning microcalorimetry, UV spectroscopy, 1H and 13C NMR, etc.

Expected results of the project are as follows:

(1) Accumulation of the data on the effect of the nature of the ionic liquid on the structure and properties of conducting polymers prepared from model compounds, such as benzene, pyrrole, thiophene, aniline, pyridine, imidazole.

(2) Synthesis of new ionic liquids with tunable acid-base and conducting properties and physicochemical characterization of the ionic liquids by the available methods.

(3) Study of the processes of polymerization of new substrates such as Buckminster fullerene and fluorinated fullerenes, as well as functionalized aromatic compounds, including esters of corresponding sulfonic acids.

(4) Elaboration of the rationale and understanding of the basic mechanisms of polymerization in ionic liquids applied to the electrocatalytic synthesis of conducting polymers.

The participation of 20 highly skilled specialists in the project will turn their activity from the development of weapons to the development of high technology. The results obtained will make it possible to produce new catalysts for environmentally important branches of industry such as manufacture of new valuable materials with tunable properties, development of wasteless and energy-saving processes of polymerization of various substrates.


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