A Tailor-Made Polymethacrylate Bearing a Reactive Diene in Reversible Diels–Alder Reaction A. AMALIN KAVITHA, NIKHIL K. SINGHA Indian Institute of Technology, Rubber Technology Centre, Kharagpur 721302, India Received 2 March 2007; accepted 30 April 2007 DOI: 10.1002/pola.22195 Published online in Wiley InterScience (www.interscience.wiley.com). ABSTRACT: A tailor-made polymethacrylate bearing a pendant furfuryl group was prepared by atom transfer radical polymerization (ATRP), an important method of recent advances in controlled radical polymerization. It was otherwise difficult to pre- pare via conventional radical polymerization, because of several side reactions involv- ing the reactive diene functionality of the furfuryl group. Successful Diels–Alder (DA) chemistry was carried out using this reactive furfuryl group of the tailor-made poly- mer as diene and a bismaleimide as a dienophile. Interestingly, the resultant mate- rial was observed to be thermoreversible as evidenced by FT-IR and DSC studies. This example of application of a tailor-made polymer having controlled molecular architecture and with reactive diene functionality in DA chemistry will open new pos- sibilities to prepare newer tailor-made reversible materials. V V C 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4441–4449, 2007 Keywords: ATRP; Crosslinking; Diblock copolymers; Diels-Alder polymers; diels– alder reaction; Radical polymerization; tailor-made polymer; thermally amendable material INTRODUCTION The Diels–Alder (DA) reaction is an important arsenal to synthetic chemists for decades. In recent years there has been extensive research in the DA reaction, because of its tremendous applications in different important areas like the synthesis of natural products, bioactive com- pounds and so forth. 1–8 Although the DA reac- tion is an interesting synthetic tool in organic chemistry its application in polymer chemistry is very scanty. The literature 9–15 in this area is only limited to preparation of polymers or mono- mers having a furan derivative and followed by reaction with a dienophile. In these cases poly- mers are prepared via conventional radical poly- merization, which leads to uncontrolled molecu- lar weight and high polydispersity index (PDI). In many cases the polymers are gelled because of side reactions involving the pendant reactive diene moieties. There are many disadvantages to carry out DA reaction in these polymers. It is difficult to study the mechanism of chemical transformation during DA reaction. It is also dif- ficult to carry out retroDA (rDA) reactions on these polymers having reactive diene moiety, as they are already gelled during polymeriza- tion. 13,16–18 It would be interesting if DA reaction is applied to the tailor-made polymers having a furfuryl group as reactive diene functionality in which necessary parameters are well-defined; like polymers have controlled molecular weight, narrow polydispersity index and well-defined end functionality and so forth. This article includes Supplementary Material available from the authors upon request or via the Internet at www. interscience.wiley.com/jpages/0887-624X /suppmat. Correspondence to: N. K. Singha (E-mail: nks@rtc.iitkgp. ernet.in) Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 45, 4441–4449 (2007) V V C 2007 Wiley Periodicals, Inc. 4441