迈克尔加成聚合.pptVIP

Michael Addition Polymerization Da Huang 2011/10/23 Content Introduction of Michael Addition Reactions Michael Addition Polymerizations Linear step growth Michael addition polymerizations Linear chain growth Michael addition polymerizations Applications of Michael addition polymerizations Michael Addition Reactions Definition: the base-catalyzed addition of a nucleophile such as an enolate (Michael donor) to an activated α,β-unsaturated carbonyl-containing compound (Michael acceptor). Classification: Carbon Michael addition. Heteroatomic (杂原子)Michael addition. Advantages: Mild reaction conditions. High functional group tolerance. A large host of polymerizable monomers. High conversions and favorable reaction rates. Mechanism Heteroatomic donors in the Michael reaction Heteroatomic donors: nucleophiles involving N, S, O, P. The aza-Michael reaction (amines) and the thiol Michael addition reaction are of primary importance due to the presence of sulfur and nitrogen nucleophiles in biological systems. The aza-Michael reaction Reactivity: secondary amines primary amines Linear step growth Michael addition polymerizations Synthesis of Poly(amino ester) via step growth Michael addition polymerization. Linear chain growth Michael addition polymerizations A classic example: the anionic chain-growth polymerization of methacrylate monomers. Applications Synthesis of linear, graft, hyperbranched, dendritic polymers. Synthesis of crosslinked polymers such as hydrogels , thermoset resins , and coatings. Bioconjugates such as polymer–protein and polymer–drug conjugates. Biomedical applications such as DNA or drug delivery, cells caffolds and tissue replacements. Different Michael donors General carbon-Michael reaction mechanistic scheme： B.D. Mather et al. / Prog. Polym. Sci. 31 (2006) 487–531 AEPZ aromatic dithiols Secondary amines are more nucleophilic B.D. Mather et