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New comonomer synthesis from thiophene-2-carbonyl chloride and cyclohexanone formaldehyde resin

Esin Ateş (Istanbul Technical University, Faculty of Science, Department of Chemistry, Istanbul, Turkey)
Nilgün Kizilcan (Istanbul Technical University, Faculty of Science, Department of Chemistry, Istanbul, Turkey)
Merve İstif (Istanbul Technical University, Faculty of Science, Department of Chemistry, Istanbul, Turkey)

Pigment & Resin Technology

ISSN: 0369-9420

Article publication date: 2 March 2015

Abstract

Purpose

The purpose of this paper is to synthesise an electro-active monomer containing ketonic resins and then to investigate the redox reaction between Fe+3 and bound thiophene in comonomer. First, thiophene-functionalised ketonic resins were synthesised by esterification reaction of thiophene-2-carbonyl chloride (ThCCl) and hydroxyl groups of cyclohexanone formaldehyde resin (CFR). Thiophene-containing cyclohexanone formaldehyde resin (Th-CFR) was then polymerised by ferric salt. The structures of the specimens were characterised by means of Fourier transform infrared and Proton – Nuclear Magnetic Resonanse (1H-NMR) spectroscopy. Thermal properties of the samples were determined with differential scanning calorimeter. Molecular weights of the specimens were determined by gel permeation chromatography. The obtained samples were also characterised morphologically by scanning electron microscope.

Design/methodology/approach

Synthesis of Th-CFR comonomers by a combination of condensation polymerization and chemical oxidation polymerisation processes is described. First, Th-CFR units were prepared by direct condensation reaction of thiophene-2-carbonyl chloride (ThCCl) and hydroxyl groups of CFR. Then, the chemical oxidation (CO) of Th-CFR in the presence of anhydrous iron (III) chloride salt (FeCl3) was performed in chloroform (CHCl3)/acetonitrile mixture solutions at room temperature.

Findings

The important structural factor determined quantitatively for Th-CFR is the CFR/ThCCl ratio after reaction. The effect of the mole ratio effect of ThCCl and ketonic resin on the solubility, molecular weight, Tm and Tg values of the comonomers (Th-CFRs) were investigated.

Research limitations/implications

The ferric ion (Fe+3) has a standard oxidation potential. Furthermore, FeCl3 can react with thiophene to produce a cation radical. FeCl3 cannot react with hydroxyl groups of ketonic resins. When ferric is used for in situ chemical oxidation application at relatively low temperatures (e.g. < 20°C), the oxidation reactions are usually less aggressive.

Practical implications

This work provides technical information for the synthesis of conducting block copolymer and for the synthesis of chain-extended resins. The modified resins contain electro-active monomer as thiophene. The chemical oxidation system has been used to polymerise these thiophene groups and resins with much higher molecular weight might be produced. These resins may also promote the adhesive strength of a coating and corrosion inhibition to metal surfaces of a coating.

Social implications

This will be used for the preparation of AB- and ABA-type block copolymers. These block copolymers may exhibit different properties due to incorporation of monomer into the block copolymer structure.

Originality/value

Novel Th-CFR comonomers were synthesised. These comonomers have higher glass transition temperature (Tg) and melting temperature (Tm) value than CFR alone. The chemical oxidation system has been used to polymerise these thiophene-functionalised ketonic resins.

Keywords

Acknowledgements

This work was financially supported by Istanbul Technical University Research Foundation (İTÜ-BAP Project No: 34,094).

Citation

Ateş, E., Kizilcan, N. and İstif, M. (2015), "New comonomer synthesis from thiophene-2-carbonyl chloride and cyclohexanone formaldehyde resin", Pigment & Resin Technology, Vol. 44 No. 2, pp. 79-86. https://doi.org/10.1108/PRT-10-2013-0091

Publisher

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Emerald Group Publishing Limited

Copyright © 2015, Emerald Group Publishing Limited