Homo and block copolymers of tert-butyl methacrylate by atom transfer radical polymerization

Atom transfer radical polymerization (ATRP) of tert-butyl methacrylate (tBMA) was investigated using cuprous bromide with different ligands, solvents, deactivators, etc. The polymerization in bulk and diphenyl ether solvent system performed using Cu(I)Br complexed with N, N, N′, N″, N″-pentamethyldi...

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Bibliographic Details
Published in:European polymer journal 2004-10, Vol.40 (10), p.2269-2276
Main Authors: Krishnan, R., Srinivasan, K.S.V.
Format: Article
Language:English
Subjects:
Applied sciences
Atom transfer radical polymerization
Block copolymers
Exact sciences and technology
Living polymerization
Organic polymers
Physicochemistry of polymers
Polymerization
Preparation, kinetics, thermodynamics, mechanism and catalysts
tert-Butyl methacrylate
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Summary:Atom transfer radical polymerization (ATRP) of tert-butyl methacrylate (tBMA) was investigated using cuprous bromide with different ligands, solvents, deactivators, etc. The polymerization in bulk and diphenyl ether solvent system performed using Cu(I)Br complexed with N, N, N′, N″, N″-pentamethyldiethylenetriamine (PMDETA) catalyst in conjunction with 2-bromopropionitrile as an initiator at room temperature showed a curvature in the first-order kinetic plot. The controlled polymerization in methanol solution resulted in slower rate of polymerization and lower molecular weights. Well-defined diblock copolymers of PSt-b-PtBMA synthesized by polystyrene bromo macroinitiator (PSt-Br) with Cu(I)Cl/PMDETA catalyst system yielded predetermined molecular weights and lower polydispersities. Otherwise, the Cu(I)Br/PMDETA catalytic system showed an inefficient polymerization of tert-butyl methacrylate with lower molecular weights and higher polydispersities. Subsequent hydrolysis of the homopolymer refluxed in dioxane with addition of HCl afforded well-defined poly(methacrylic acid).
ISSN:0014-3057
1873-1945
DOI:10.1016/j.eurpolymj.2004.06.010