Crosslinking polymerization leading to interpenetrating polymer network formation. 3. Polyaddition Crosslinking reaction of poly(methyl methacrylate-co-2-methacryloyloxyethyl isocyanate) with poly(oxytetramethylene) glycol in the presence of linear p

摘要

As part of a series of our works concerned with the elucidation of the crosslinking polymerization mechanism leading to the interpenetrating polymer network (IPN) formation, in which IPN consists of both polyurethane (PU) and polymethacrylate (PM) networks, this article deals with the polyaddition crosslinking reactions of poly(methyl methacrylate-co-2-methacryloyloxyethyl isocyanate) poly-(MMA-co-MOI) [MMA/MOI = 99/1] as a novel multifunctional polyisocyanate with poly(oxytetramethylene) glycol [H-(OCH2CH2CH2CH2)(n)-OH (n = 28)] (POTMG-28) in the presence of two types of linear PMs, differently miscible with the resulting PU networks, leading to semi-IPN formation. Thus, poly(MMA-co-MOI) was prepared by the radical copolymerization of MOI with MMA in the presence of CBr4 as a chain-transfer agent. No influence of the linear PM on the rate of polyaddition crosslinking reaction was observed. The actual gel points were compared with the theoretical ones calculated according to Macosko's equation: the deviation of the actual gel point from the theoretical one was rather small, close to the ideality, and the delayed gelation from theory tended to become a little smaller in the presence of PM. These are discussed mechanistically to deepen the understanding of the PU network formation in the presence of a linear PM resulting in semi-IPN, along with the data of the intrinsic viscosities of resulting prepolymers. To collect a direct evidence of semi-IPN formation, we attempted to pursue the incorporation of the linear PM into the resulting PU networks by H-1-NMR and UV-vis spectroscopy; in the latter case, the copolymers containing a small amount of pyrenyl methacrylate were used as linear PMs because the pyrenyl group was employed as the probe for UV-vis spectroscopic determination of the amount of the incorporated PM. The swelling ratio of the gel became lower in the presence of a linear PM. All data for the polyaddition crosslinking reactions of poly(MMA-co-MOI) with POTMG-28 in the presence of PM, along with the mechanistic discussion, demonstrate that the freely compatible molecular interaction would lead to a true semi-IPN formation as a result of the good miscibility between PU networks and a linear PM. (C) 2004 Wiley Periodicals, Inc.