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  • 1.
    Bergenudd, Helena
    et al.
    KTH, Skolan för kemivetenskap (CHE), Kemi, Kärnkemi.
    Coullerez, Geraldine
    KTH, Skolan för kemivetenskap (CHE), Kemi, Kärnkemi.
    Jonsson, Mats
    KTH, Skolan för kemivetenskap (CHE), Kemi, Kärnkemi.
    Malmström, Eva E.
    KTH, Skolan för kemivetenskap (CHE), Fiber- och polymerteknik.
    Solvent Effects on ATRP of Oligo(ethylene glycol) Methacrylate. Exploring the Limits of Control2009Inngår i: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 42, nr 9, s. 3302-3308Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Five copper complexes in combination with six monomer-solvent mixtures have been used to investigate the solvent effects oil ATRP of oligo(ethylene glycol) methacrylate (OEGMA). The redox properties of the copper complexes in OEGMA-solvent mixtures and the apparent rate constants (k(p)(app)) for ATRP of OEGMA were correlated to the degree of control over the polymerizations. Based on this correlation, a general discussion of the limits of control in ATRIP is carried out. One of the key parameters for control in ATRP is the propagation rate constant, making the choice of monomer essential for the design of ail ATRP system. Also, the solvent effects oil the ATRP equilibrium constant (K-ATRP) affect the limit of control (i.e., the apparent rate constant above which control is lost). The choice of copper complex is also more important than the choice of solvent for the design of a well-controlled ATRP system.

  • 2.
    Coullerez, Geraldine
    et al.
    KTH, Tidigare Institutioner, Fiber- och polymerteknologi.
    Carlmark, Anna
    KTH, Tidigare Institutioner, Fiber- och polymerteknologi.
    Malmström, Eva
    KTH, Tidigare Institutioner, Fiber- och polymerteknologi.
    Jonsson, Mats
    KTH, Tidigare Institutioner, Kemi.
    Understanding copper-based atom-transfer radical polymerization in aqueous media2004Inngår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 108, nr 35, s. 7129-7131Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    This study investigates the mechanism of copper(I)-mediated living atom-transfer radical polymerization (ATRP) in aqueous media. It is shown that the ATRP apparent rate constant for polymerization of methoxycapped oligo(ethylene glycol) methacrylate (OEGMA) in water (k(P)(app)) at room temperature correlates with the redox potential (E-1/2) of the copper complexes. The results are discussed along with previously published results on the kinetics for bulk polymerization of methyl acrylate at 60 degreesC with the redox potentials measured in MeCN. The faster ATRP kinetics in water can mainly be attributed to a higher equilibrium concentration of propagating radicals [W] and to solvent effects on the rate of propagation k(p). It is shown that [R*] can be calculated from the redox properties of the alkyl halide and the copper complex. The values of [R*] in MeCN/bulk and in H2O were determined to be 8.2 x 10(-8) and 6.3 x 10(-5) M, respectively. The respective kp values are in good agreement with the literature values (3.6 x 10(3) M-1 s(-1) for OEGMA in water and 2.5 x 10(3) M-1 s(-1) for methyl acrylate in bulk).

  • 3.
    Coullerez, Geraldine
    et al.
    KTH, Skolan för kemivetenskap (CHE), Kemi, Kärnkemi. KTH, Skolan för kemivetenskap (CHE), Fiber- och polymerteknik.
    Malmström, Eva
    KTH, Skolan för kemivetenskap (CHE), Fiber- och polymerteknik.
    Jonsson, Mats
    KTH, Skolan för kemivetenskap (CHE), Kemi, Kärnkemi.
    Solvent effects on the redox properties of Cu complexes used as mediators in atom transfer radical polymerization2006Inngår i: Journal of Physical Chemistry A, ISSN 1089-5639, E-ISSN 1520-5215, Vol. 110, nr 34, s. 10355-10360Artikkel i tidsskrift (Fagfellevurdert)
    Abstract [en]

    Solvent effects on the redox properties of six Cu(I) complexes used as mediators in atom transfer radical polymerization (ATRP) have been studied using cyclic voltammetry. The six ligands used were tris[2(dimethylamino) ethyl] amine, N-(n-propyl)-2-pyridylmethanimine, N, N, N', N', N'-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyl-triethylenetetramine, 2,2'-bipyridine, and 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecan. The solvents used were DMSO, DMF, MeCN, MeOH, IP, and BuOH. Significant solvent effects were observed and quantitatively analyzed in terms of Kamlet-Taft relationships. The resulting Kamlet-Taft equations were found to successfully describe the solvent effects and could thus be used as tools for the design of ATRP in new solvents. The solvent sensitivity of the different ligands and the nature of the solvent effects are also discussed to some extent.

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