화학공학소재연구정보센터
Macromolecules, Vol.44, No.18, 7115-7123, 2011
Reactive Polyanions Based on Poly(4,4-dimethyl-2-vinyl-2-oxazoline-5-one-co-methacrylic acid)
The formation of reactive polyanions by semi-batch copolymerization of 4,4-dimethyl-2-vinyl-2-oxazoline-5-one (VDMA) and methacrylic acid (MAA) by both free radical and photoinduced radical polymerization is described. The reactivity ratios of these two monomers were determined to be 1.36 and 0.41 for r(1)(VDMA) and r(2)(MAA), respectively, using (1)H NMR spectroscopy. During the free radical copolymerization of a 50:50 VDMA:MAA copolymer (PMV(50)) in anhydrous DMSO or THF at 60 degrees C, up to 40% of the azlactone groups in the copolymer are hydrolyzed by water formed largely by conversion of methacrylic acid diads into cyclic anhydride. Storage in organic solutions leads to further transhydration, while solid PMV(50), is stable for at least 6 months at room temperature. Increasing the VDMA comonomer content reduces this transhydration, likely through decreasing the incidence of methacrylic acid diads in the backbone. Alternatively, conducting the copolymerization at 20 degrees C using photoinitiation is also effective at suppressing this transhydration. The resulting reactive polyanions bind under physiological conditions to poly-L-lysine-coated calcium alginate hydrogel beads and spontaneously cross-link with the polyamine to form covalent networks of interest for long-term therapeutic cell encapsulation. This represents the first such use of a VDMA-containing polyanion in aqueous environments. The copolymers were characterized by (1)H NMR, quantitative (13)C NMR, (13)C DEPT-135 NMR, and FT-IR spectroscopies as well as by elemental analysis.
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