Novel comonomer synthesis from thiophene-2-carbonyl chloride and polydimethylsiloxane modified cyclohexanone formaldehyde resin

Abstract

Purpose

The purpose of this paper is to produce an electroactive monomer containing ketonic resins and then to investigate redox reaction between Fe+3 and bounded thiophene in comonomers. First, thiophene functionalised ketonic resins (Th-CFPDMSR) were synthesised by esterification reaction of thiophene-2-carbonyl chloride (ThCCl) and hydroxyl groups of cyclohexanone formaldehyde resin (CFR). Th-CFPDMSR was then polymerised by ferric salt. Thiophene modified ketonic resins (Th-CFPDMSR) as comonomers were characterised by common techniques such as gel permeation chromatography, proton nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimeter and scanning electron microscope.

Design/methodology/approach

Th-CFPDMSR comonomers were synthesised by esterification reaction of ThCCl and hydroxyl groups of ketonic resins. Then, the in-situ chemical oxidation (ISCO) of ThC-CFR in the presence of iron (III) chloride salt (FeCl3) was accomplished in chloroform/acetonitrile mixture solutions at room temperature.

Findings

Important structural factor determined quantitatively for Th-CFPDMSR is the CFPDMS/TCCl ratio after reaction. The mole ratio effect of TCCl and ketonic resin on the solubility, molecular weight, melting temperature (Tm) and glass transition temperature (Tg) values of the comonomers (TCCl-CFPDMSR) was 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 ISCO 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 thiophene. The chemical oxidation system has been used to polymerise these thiophene groups, and resins with much higher molecular weight might be produced. The resins may also promote the adhesive strength of a coating and corrosion inhibition to metal surfaces of a coating.

Originality/value

Novel Th-CFPDMSR comonomers were synthesised. These comonomers have higher Tg and Tm values than CF-PDMSR alone. The chemical oxidation system has been used to polymerise these thiophene functionalised ketonic resins.

Citation

Kizilcan, N. and Istif, M. (2014), "Novel comonomer synthesis from thiophene-2-carbonyl chloride and polydimethylsiloxane modified cyclohexanone formaldehyde resin", Pigment & Resin Technology, Vol. 43 No. 5, pp. 277-284. https://doi.org/10.1108/PRT-07-2013-0055