Monomers for Adhesive Polymers 12 Synthesis and Free-Radical Homo- and Copolymerization of 2-Ethoxycarbonylallyl 5-(1,2-dithiolane-3-yl)-pentanoate

• Published in: Macromolecular materials and engineering Vol. 298; no. 11; pp. 1220 - 1231
• Main Authors: Pavlinec, Juraj, Kleinova, Angela, Angermann, Jörg, Lamparth, Iris, Moszner, Norbert
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 01.11.2013; WILEY‐VCH Verlag; Wiley; John Wiley & Sons, Inc
• Subjects: adhesives; Applied sciences; Argon oxygen decarburizing; Chains (polymeric); Copolymerization; Crosslinking; dental polymers; disulfides; Exact sciences and technology; Free radicals; Initiators; kinetics of polymerizations; Monomers; Organic polymers; Physicochemistry of polymers; Polymerization; Polymers; Preparation, kinetics, thermodynamics, mechanism and catalysts; Solvents; Thiol polymer; monomers; Solution polymerization; Crosslinked copolymer; disulfides; Organic disulfide; kinetics of polymerizations; Crosslinked polymer; Thiol copolymer; Acrylic polymer; Monomer; Chemical reactivity; Adhesive; Acrylic copolymer; dental polymers; Dithiol; adhesives; Bifunctional compound; Solution copolymerization; Experimental study; Methyl methacrylate copolymer; Reaction rate; Reactivity ratio; Free radical polymerization; Radical copolymerization
• ISSN: 1438-7492; 1439-2054
• DOI: 10.1002/mame.201200382

The 2‐ethoxycarbonylallyl 5‐(1,2‐dithiolane‐3‐yl)‐pentanoate monomer (AODS) includes in its molecular structure CC and SS reactive bonds allowing it to behave as a bi‐functional monomer, possessing two groups, however, with different reactivity for use in polymer chain building. The polymerization‐specific features of this monomer are the absence of auto‐acceleration and polymer chain crosslinking. Polymerization proceeds readily through most free‐radical initiators. One exception, carboxy‐peroxides are rapidly decomposed without the production of free radicals. AODS is partially converted to a gel without the consumption of double bonds during monomer dissolution in certain organic solvents and after being mixed in solution with carboxy‐peroxides. The determined AODS‐co‐MMA copolymerization parameters are r1 = 2.61, r2 = 0.23 if Luperco peroxide is used as a polymerization initiator, and r1 = 2.71, r2 = 0.38 if AIBN is used. The 2‐ethoxycarbonylallyl 5‐(1,2‐dithiolane‐3‐yl)‐pentanoate monomer (AODS) easily polymerizes in the presence of most free‐radical initiators with the exception of carboxy‐peroxides. Vinyliden along with dithiolane disulfide bonds provide the monomer AODS entry into polymer chains and crosslinks through C–C and S–S bonds. The polymer gels are formed spontaneously in polar solvents or by mixing with carboxy‐peroxides. The monomer intra‐ to inter‐molecular disulfide bonds rearrangement is assumed.