Synthesis of a [60]fullerene‐functionalized poly(vinyl chloride) derivative by stereospecific chemical modification of PVC

Abstract

The covalent attachment of [60]fullerene (C60) to two poly(vinyl chloride) (PVC) samples with different isotactic content is achieved by direct reaction in o‐dichlorobenzene (o‐DCB) solution in the presence of AIBN. The extent of fullerenation is controlled by varying the C60 feed ratio. The pendant C60‐chemically modified PVC polymers are soluble in tetrahydrofuran (THF) and have been characterized by UV–vis, NMR, FTIR, DSC, TGA, cyclic voltammetry, and SEM. The quantitative microstructural analysis after covalent attachment of the bulky C60 moiety to the PVC has been followed by 13C NMR spectroscopy. From the results it can be concluded that the modification of PVC by graft reaction through free radical reaction proceeds by a stereoselective mechanism. This conclusion has been confirmed on the basis of the increase of the glass‐transition temperature (Tg) and the thermal stability of the C60‐chemical modified PVC samples. The fullerenated PVCs obtained show good electron acceptor properties, as evidenced by electrochemical investigations. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5408–5419, 2007

Synthesis and characterization of fullerene functionalized poly(vinyl chloride) (PVC) and dehydrochlorinated PVC using atom Transfer Radical Addition and AIBN based fullerenation

“…This was not the case for the AIBN based fullerene grafted PVC (PVC‐N5) where the thermal stability was improved as compared to that of the neat PVC sample. The similar effect was reported by Martinez et al In our opinion, the discrepancy between thermal stability of ATRA based‐ and AIBN based fullerene grafted PVC might be attributed to the different content and distribution of fullerene on the polymer chains. This is an aspect deserving further investigation and clarification.…”

“…An additional small signal at around 3.9 ppm can be observed in all cases. This can be ascribed to the fulleryl protons . Similar peak was noted from the NMR spectrum of DH‐PVC (DH‐PVC‐N12).…”

“…This implies a reaction between PVC and oxygen during fullerenation. In this context, it is possible that some residual oxygenated species contained within the chemicals (solvent, initiator) can be capable of reacting with the dehydrochlorinated PVC during the fullerention, which incidentally was carried out at a relatively high temperature (80°C) compared to a lower value (70°C) used by Martinez et al (60°C) …”

“…In this regard, attachment of C 60 onto PVC molecules is now routinely carried out by the free radical approach, and by using chemical initiators. In this context, Tang et al and Martinez et al synthesized C 60 functionalized PVC through a direct chemical reaction between PVC and C 60 , using AIBN (2,2′‐azoisobutyronitrile) as the initiator. In the latter case, some useful and enhanced properties of the modified PVC were observed.…”

α‐Thiophene end‐capped styrene copolymer containing fullerene pendant moieties: Synthesis, characterization, and gas sensing properties

“…The electrochemical properties of C 60 and P3 were investigated by cyclic voltammetry in 1,2‐dichlorobenzene as a further proof for attachment of C 60 to the polymer as a side group . It is well known that C 60 has multiple and reversible redox behavior . As seen in Figure in potential range between 1 V and −3,5 V C 60 has shown triple reversible peaks on the contrary P3 has shown triple irreversible peaks.…”