2-Furfuryl methacrylate, radical

In order to study elastomeric networks, simulating the type of polymers used for tires, we switched to polymers with low glass transition temperatures and oligoether bis-maleimides. A typical random copolymer structure, built from the radical copolymerization of n-hexyl acrylate and 2-furfuryl methacrylate, is shown below. These reactions were conducted in toluene at 80°C with AIBN as initiator. After 8 h, the copolymers were recovered by precipitation in 70 to 80% yields. The compositions varied fi om 2 to 30% of the furanic monomer (monomer feed and copolymer composition were always very similar, suggesting that ri and ti must have both been close to unity). The corresponding Tgs went from -70 to 30°C for molecular weights of about 20,000. Both homopolymers were also prepared as reference materials. 

The furfuryl esters of acrylic and methacrylic acid polymerize via a free-radical mechanism without apparent retardation problems arising from the presence of the furan ring. Early reports on these systems described hard insoluble polymers formed in bulk polymerizations and the cross-linking ability of as little as 2% of furfuryl acrylate in the solution polymerization of methylacrylate121. ... 

Finally, addition polymerization of suitably substituted furans allows incorporation of the furan nucleus into heterocyclic polymers (77MH1102). 2-Vinylfuran apparently exhibits free radical polymerizability comparable with that of styrene, although rates, yields and degrees of polymerization are low under all conditions except for emulsion polymerization. Cationic polymerization is quite facile and leads not only to the poly(vinylfuran) structure (59), as found in free radically produced polymers, but also to structures such as (60) and (61) in which the furan nucleus has become involved. Furfuryl acrylate and methacrylate undergo free radical polymerization in the manner characteristic of other acrylic esters. 

Unit variability due to different ligand environments about the metal is a relatively widely distributed type of anormaly. For example, it was formd by IR and H-NMR spectroscopy that the equilibrium shown in scheme 22 occurs in a Ti(OBu)4-unsaturated alcohol system. In that scheme R OH is the monomethacrylate of ethylene glycol (2-hydroxyethyl methacrylate, MEG), furfuryl alcohol, propargyl alcohol, and 2-methylhex-5-en-3-yn-2-ol (CH2=CHC=CC(Me)20H). The Ti-O-Bu bond in Ti" + alkoxides is rather labile, which is confirmed by fast radical exchange as measured on the NMR time scale. 

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