Synthesis of telechelic oligomers by atom transfer radical polymerization: A study of acrylate monomers

Different acrylate oligomers were synthesized by atom transfer radical polymerization in the presence of a transfer agent and CuBr/1,1,4,7,10,10-hexamethyltriethylenetetramine. The functionality in bromine was determined by 1H NMR. These oligomers were coupled in the presence of Cu(0) and the ligand 2,2′-bipyridine. The coupling yield was determined by size exclusion chromatography and NMR analysis and depended on the nature of the monomer and not on the molecular weight. In other words, the preliminary functionalization of the brominated chain end with styrene increased the coupling yield. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2377-2394, 2005

[1]  Krzysztof Matyjaszewski,et al.  Polystyrene with designed molecular weight distribution by atom transfer radical coupling , 2004 .

[2]  B. Boutevin,et al.  Synthesis of Telechelic Oligomers via Atom Transfer Radical Polymerization, 1 , 2004 .

[3]  Y. Yagcı,et al.  Synthesis and Characterization of α,ω‐Telechelic Polymers by Atom Transfer Radical Polymerization and Coupling Processes , 2003 .

[4]  W. J. Simonsick,et al.  Studies of higher temperature polymerization ofn-butyl methacrylate andn-butyl acrylate , 2002 .

[5]  P. Lacroix-Desmazes,et al.  Use of Fluorinated Organic Compounds in Living Radical Polymerizations , 2002 .

[6]  M. Sawamoto,et al.  Metal-catalyzed living radical polymerization. , 2001, Chemical reviews.

[7]  K. Matyjaszewski,et al.  Controlled/living radical polymerization in aqueous media: homogeneous and heterogeneous systems , 2001 .

[8]  K. Matyjaszewski,et al.  Atom transfer radical polymerization. , 2001, Chemical reviews.

[9]  B. Boutevin,et al.  Synthesis of carboxy‐telechelic oligostyrene by dead‐end polymerization: Evaluation of primary radical termination by kinetic study and kinetic simulation model , 2001 .

[10]  A. Müller,et al.  New Strategy for the Synthesis of Halogen-Free Acrylate Macromonomers by Atom Transfer Radical Polymerization , 2001 .

[11]  A. Herk Pulsed initiation polymerization applied to acrylate monomers: Sources of experimental failure , 2001 .

[12]  K. Matyjaszewski,et al.  Functional polymers by atom transfer radical polymerization , 2001 .

[13]  A. Müller,et al.  Evidence for chain transfer in the atom transfer radical polymerization of butyl acrylate , 2000 .

[14]  P. J. Pomery,et al.  Free radical polymerization of cyclohexyl acrylate involving interconversion between propagating and mid-chain radicals , 2000 .

[15]  P. J. Pomery,et al.  Radical polymerization of phenyl acrylate as studied by ESR spectroscopy: Concurrence of propagating and mid-chain radicals , 2000 .

[16]  P. Kubisa,et al.  Studies of atom transfer radical polymerization (ATRP) of acrylates by MALDI TOF mass spectrometry , 2000 .

[17]  P. Lovell,et al.  Chain transfer to polymer in free-radical solution polymerization of 2-ethylhexyl acrylate studied by NMR spectroscopy , 1998 .

[18]  D. Paquet,et al.  Determination of Free-Radical Propagation Rate Coefficients of Butyl, 2-Ethylhexyl, and Dodecyl Acrylates by Pulsed-Laser Polymerization , 1996 .

[19]  R. Jerome,et al.  SAXS analysis of hyperstructure in carboxylato-telechelic poly(tert.butyl acrylate)'s , 1993 .

[20]  R. Jerome,et al.  Small-angle X-ray scattering study of carboxylato-telechelic poly(tert-butyl acrylate)s , 1993 .

[21]  G. Wegner,et al.  Synthesis of telechelic poly(p-phenylene) derivatives , 1992 .

[22]  J. Kennedy,et al.  Designed Polymers by Carbocationic Macromolecular Engineering , 1992 .

[23]  A. K. Banthia,et al.  Synthesis, Characterization, and Evaluation of Telechelic Acrylate Oligomers and Related Toughened Epoxy Networks , 1989 .

[24]  P. Hodge,et al.  Preparation of terminally functionalized (telechelic) methyl methacrylate oligomers by the oxidative cleavage of statistical methyl methacrylate/diene copolymers with ozone , 1989 .

[25]  W. Heitz Synthesis of telechelics and telomers by radical polymerization , 1987 .

[26]  W. Heitz,et al.  Telechelics 6. Oligostyrenes by radical polymerization , 1981 .

[27]  W. Heitz,et al.  Telechele oligomere, 2. Oligoäthylene durch radikalische polymerisation mit aibn oder dialkylperoxydicarbonat als initiator†‡ , 1976 .

[28]  O. Pierce,et al.  Coupling of monobromoperfluoroalkanecarboxylic esters , 1968 .

[29]  A. J. Costanza,et al.  Bis‐type modifiers in polymerization. I. Behavior of various disulfides in bulk styrene polymerization , 1955 .

[30]  R. Haszeldine Fluoro-olefins. Part IV. Synthesis of polyfluoroalkanes containing functional groups from chlorotrifluoroethylene, and the short-chain polymerisation of olefins , 1955 .

[31]  E. Kovach,et al.  Preparation and Properties of Some New Chelating Agents1 , 1954 .

[32]  A. L. Henne,et al.  The Direction of Addition to CFCl=CF2 under Free Radical Conditions1 , 1951 .