Crosslinking polymerization leading to interpenetrating polymer network formation. II. Polyaddition crosslinking reactions of poly(methyl methacrylate‐co‐2‐methacryloyloxyethyl isocyanate) with various diols

Abstract

As part of our continuing studies concerned with the elucidation of the crosslinking polymerization mechanism leading to interpenetrating polymer network (IPN) formation, in which IPNs consist of both polymethacrylates and polyurethane (PU) networks, this article explores the polyaddition crosslinking reactions of multifunctional poly(methyl methacrylate‐co‐2‐methacryloyloxyethyl isocyanate) [poly(MMA‐co‐MOI)] [MMA/MOI = 90/10] with various diols leading to PU network formation. Thus, the equimolar polyaddition crosslinking reactions of poly(MMA‐co‐MOI) with ethylene glycol (EG), 1,6‐hexane diol, and 1,10‐decane diol (DD) were carried out in N‐methyl pyrrolidone at a 0.25 mol/L isocyanate group concentration at 80 °C. The second‐order rate constants decreased from EG to DD. The deviation of the actual gel point from the theoretical one was smaller from EG to DD. The intrinsic viscosity of resulting prepolymer demonstrated almost no variation with progressing polymerization for the EG system, whereas it gradually increased with conversion for the DD system. Close to the gel point conversion it increased rather drastically for both systems. The swelling ratio of resulting gel was higher from EG to DD. These are discussed mechanistically in terms of the significant occurrence of intramolecular cyclization and intramolecular crosslinking reactions leading to shrinkage of the molecular size. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3243–3248, 2003

Stable heterocumulene monomer in water; Synthesis and polymerization of (meth)acrylates having an isothiocyanate structure

“…[4][5][6] However, isocyanate is highly labile to water and difficult to be handled. To synthesize isocyanate containing clear homopolymer, completely dry solvent and technological excellence are necessary.…”

Selective nucleophilic additions to poly(methacrylate)s containing isothiocyanate moieties in the side chains and their application in cross-linking

“…Isocyanate‐containing monomers are popular monomers manufactured in an industrial scale, which are useful because one can easily introduce reactive isocyanato groups into various vinyl polymers by copolymerization, or transform various amines and alcohols to polymerizable monomers by connecting at the isocyanato moiety . However, isocyanate is highly labile to water and difficult to handle.…”

Effect of primary polymer chain rigidity on intramolecular cyclization and intramolecular crosslinking in free‐radical crosslinking monomethacrylate/dimethacrylate copolymerizations

“…d ‐Bornyl methacrylate (BoMA) was chosen as a typical example of bulky monomethacrylate monomers, the polymerization of which leads to the formation of rigid polymer chain. Besides, this work provides useful information for a full understanding of three‐dimensional network formation in free‐radical crosslinking monovinyl/divinyl copolymerizations as part of our continuing studies aimed at the elucidation of the crosslinking polymerization mechanism and the control of network formation to molecularly design a variety of network polymers 1, 33–37…”