Zirconocene‐catalyzed copolymerization of methyl methacrylate with other methacrylate monomers

Abstract

Statistical copolymers of methyl methacrylate (MMA) with n‐butyl‐, s‐butyl, t‐butyl‐, n‐hexyl‐, decyl‐, stearyl‐, allyl‐, trimethylsilyl‐ and trimethylsilyloxyethyl methacrylate were prepared by zirconocene‐catalyzed copolymerization. The reactivity ratios of MMA copolymers with butyl‐, hexyl‐, and stearyl methacrylate were estimated using the Finemann–Ross, the inverted Finemann–Ross, and the Kelen–Tüdos graphical methods. Structural parameters of the copolymers were obtained from the calculated dyad sequences, derived by using the reactivity ratios. The effect of the nature of the methacrylate ester group and the catalytic system used on the copolymer structure is discussed. The glass‐transition temperature (Tg) values of MMA copolymers with butyl‐ and hexyl methacrylate were measured and examined in the frame of several theoretical equations, allowing the prediction of these Tg values. The best fit was obtained using Barton and Johnston equations, taking the monomer sequence distribution of the copolymers into account. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3761–3774, 2004

Poly(ethyl methacrylate-co-hydroxyethyl acrylate) random co-polymers: Dielectric and dynamic-mechanical characterization

“…The monomer sequence distribution, determined by the reactivity ratios, also may affect the glass transition temperature due to the change in the interactions between adjacent monomeric units along the chain. This effect can be enhanced when one of the monomers presents a strong permanent dipolar moment while the other is not polar [4,5]. The influence of this effect on the composition dependence of T g can also be taken into account in the empirical equations [6,7].…”

Synthesis of amphiphilic block copolymers via ring opening polymerization and reversible addition‐fragmentation chain transfer polymerization

“…An alternative route involves the use of so-called organocatalysts, of which the first, 4-dimethylaminopyridine (DMAP), was introduced in 2001 by Nederberg et al 29 Since then, a wide variety of classes of organocatalysts, such as N-heterocyclic carbenes (NHCs), acid catalysts like diphenyl phosphate (DPP), bifunctional thiourea-amine systems, as well as guanidines and amidines, have emerged. [30][31][32][33][34][35] While NHCs represent the most extensively studied family of organocatalysts, the guanidine and amidine superbases such as 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,-5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), and 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU) have also been of considerable interest. The mechanism of DBU-catalyzed ROP of lactide in particular has been intensively investigated in recent years.…”

“…In addition, the complete removal of the metal catalyst cannot always be guaranteed, which leads to concerns if the polymers are to be used for biomedical applications. An alternative route involves the use of so‐called organocatalysts, of which the first, 4‐dimethylaminopyridine (DMAP), was introduced in 2001 by Nederberg et al 29 Since then, a wide variety of classes of organocatalysts, such as N ‐heterocyclic carbenes (NHCs), acid catalysts like diphenyl phosphate (DPP), bifunctional thiourea‐amine systems, as well as guanidines and amidines, have emerged 30–35 . While NHCs represent the most extensively studied family of organocatalysts, the guanidine and amidine superbases such as 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD), 7‐methyl‐1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (MTBD), and 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) have also been of considerable interest.…”

Influence of the cocatalyst structure on the statistical copolymerization of methyl methacrylate with bulky methacrylates using the zirconocene complex Cp2ZrMe2

“…Polar monomers and especially methacrylates were not reported, even though experimental data on the copolymerization of such monomers with other methods (radical polymerization, atom transfer radical, anionic, alkyllithium/trialkyl aluminum initiated, and group transfer)10 had been known for quite some time. Only very recently did Hadjichristidis et al11 report the copolymerization of MMA with other methacrylates, with n ‐alkyl side groups, in a study that involved the determination of the reactivity ratios, mean sequence lengths, and monomer dyad distributions in the produced copolymers.…”