0000000000121528
AUTHOR
Wolfgang Radke
Hyperbranched methacrylates by self-condensing group transfer polymerization
The synthesis of hyperbranched methacrylates was achieved by self-condensing group transfer polymerization of 2-(2-methyl-1-triethylsiloxy-1-propenyloxy)ethyl methacrylate (1). “Back-biting” is shown to be the predominant side reaction. In spite of this, the compact nature of the hyperbranched molecules was demonstrated through SEC-viscosity measurements and comparison with a linear analogue. The degree of branching can be controlled by copolymerization with conventional monomers, e.g. MMA, and the living polymers can be used as macroinitiators for star-shaped polymers.
Estimation of Number-Average Molecular Weights of Copolymers by Gel Permeation Chromatography−Light Scattering
The true number-average molecular weight, Mn, of copolymers is obtained by GPC coupled with a light-scattering detector even if the composition and therefore the refractive index increment varies with elution volume, provided slices taken are monodisperse with respect to molecular weight and composition. In contrast, only an apparent weight-average molecular weight, can be obtained by the conventional GPC−light scattering combination, even for a perfect chromatographic resolution. The errors in Mn associated with nonhomogeneous slices are estimated. Experimental data with mixtures of linear polystyrene and poly(methyl methacrylate) confirm these estimations and indicate that the error in Mn…
Acrylic Graft Copolymers Via Macromonomers
Comb-shaped poly(methyl methacrylate) (PMMA) and PMMA grafted with poly(nbutyl acrylate) (PnBuA) were prepared by radical copolymerisation of ω-methacryloyl-PMMA with MMA and nBuA, respectively. The comb-shaped PMMA is characterised with respect to radius of gyration by using GPC equipped with a multi-angle laser light scattering detector. The radical copolymerisation of the macromonomer with nBuA in toluene follows complex kinetics. The dependence of the relative reactivity of the macromonomer on absolute concentration and on the ratio of comonomers may be explained by preferential solvation of comonomers by segments of their own kind (“bootstrap effect”) or even micelle formation. However…
Mean square radius of gyration and hydrodynamic radius of jointed star (dumbbell) and H-comb polymers
Equations for the mean square radius of gyration and the hydrodynamic radius for jointed stars (dumbbells) and H-combs are derived, based on random flight statistics for each subchain. Comparision with literature data on computer simulations and experimental data for H-combs show good agreement for the g-value of the mean square radius of gyration even in good solvents. This suggests that for the mean square radius of gyration the relative dimension of a H-comb relative to the linear molecule of the same degree of polymerization is not altered significantly by long range interactions, as in the case of star polymers. For the hydrodynamic radius the situation is different. Fair agreement is …
Copolymerization of methacryloyl-terminated PMMA macromonomers with methyl methacrylate
Methacryloyl-terminated macromonomers (MM) of polymethylmethacrylate (PMMA) of two different molecular weights were prepared by group transfer polymerization (GTP). They were copolymerized with methyl methacrylate (MMA) by radical polymerization using toluene as the solvent. The relative reactivity of the MM, 1/r1, decreases with increasing initial MM concentration. This is interpreted as a consequence of the increasing viscosity of the reaction medium leading to an increasing diffusion control of the MM addition. At a constant weight ratio of MMA to MM the reactivity of the longer macromonomer is higher than of the shorter one. Increasing the molar ratio [MMA]/[MM], i.e. increasing the ave…
Acrylic thermoplastic elastomers and comb-shaped poly(methyl methacrylate) via the macromonomer technique
Comb-shaped poly(methyl methacrylate) (PMMA) and poly(butyl acrylate) (PnBuA) grafted with PMMA were prepared by radical copolymerization of ω-methacryloyl-PMMA with MMA and nBuA, respectively. The comb-shaped PMMA is characterized with respect to radius of gyration by using gel permeation chromatography equipped with a multi-angle laser light scattering detector. The radical copolymerization of the macromonomer with nBuA in toluene follows complex kinetics. The dependence of the relative reactivity of the macromonomer on absolute concentration and on the ratio of comonomers may be explained by preferential solvation of comonomers by segments of their own kind (“bootstrap effect”) or even m…
Effect of core-forming molecules on molecular weight distribution and degree of branching in the synthesis of hyperbranched polymers
The polydispersity index, the molecular weight distribution (MWD), and the degree of branching ( ) are calculated for hyperbranched polymers obtained in self-condensing vinyl polymerization of AB* monomers in the presence of a core-forming molecule (i.e. a multifunctional initiator, Bf*). Two cases are considered: (a) batch polymerization, i.e., with all components mixed together; (b) semibatch polymerization, i.e., slow addition of the monomer to the core-forming molecule. The results obtained for the latter case are also valid for polycondensation of AB2 monomers. The presence of core-forming molecules leads to a considerable narrowing of the MWD's, the polydispersity index decreasing wi…