Research on “post‐metallocene” polymerization catalysis ranges methodologically from fundamental mechanistic studies of polymerization reactions over catalyst design to material properties of the polyolefins prepared. A common goal of these studies is the creation of practically useful new polyolefin materials or polymerization processes. This Review gives a comprehensive overview of post‐metallocene polymerization catalysts that have been put into practice. The decisive properties for this success of a given catalyst structure are delineated.

Highly fluorescent conjugated polymer nanoparticles were prepared directly by polymerization in aqueous miniemulsion, employing Glaser coupling polymerization as a suitable step-growth reaction. A 4,4'-dinonyl-2,2'-bipyridine-modified catalyst was found to be suited for the polymerization in the aqueous heterophase system. Nanoparticles of poly(arylene diethynylenes) (arylene = 2,5-dialkyoxy phenylenes and 9,9'-dihexyl fluorene) with molecular weights in the range of M(n) 10(4) to 10(5) g mol(-1) and with sizes of < or = 30 nm, as observed by TEM, result. N,N'-di(4-ethynylphenyl)-1,7-di[4-(1,1,3,3-tetramethylbutyl)phenoxy]perylene-3,4:9,10-tetracarboxdiimide or 2,7-diethynylfluorenone was converted completely during the heterophase polymerization to afford colloidally stable nanoparticles of poly(arylene diethynylenes) with 0.1-2 mol % covalently incorporated perylene dye and 2-9 mol % of covalently incorporated fluorenone dye, respectively. Fluorescence spectroscopy of the aqueous dispersions reveals an efficient energy transfer to the dye in the nanoparticles, which enables a variation of the luminescence emission color between red (lambda(em) (max.) ca. 650 nm) and the green emission of the nanoparticles without dye.

Single-molecule fluorescence microscopy was used to investigate the dynamics of perylene diimide (PDI) molecules in thin supported polystyrene (PS) films at temperatures up to 135 °C. Such high temperatures, so far unreached in single-molecule spectroscopy studies, were achieved using a custom-built setup which allows for restricting the heated mass to a minimum. This enables temperature-dependent single-molecule fluorescence studies of structural dynamics in the temperature range most relevant to the processing and to applications of thermoplastic materials. In order to ensure that polymer chains were relaxed, a molecular weight of 3000 g/mol, clearly below the entanglement length of PS, was chosen. We found significant heterogeneities in the motion of single PDI probe molecules near T(g). An analysis of the track radius of the recorded single-probe molecule tracks allowed for a distinction between mobile and immobile molecules. Up to the glass transition temperature in bulk, T(g,bulk), probe molecules were immobile; at temperatures higher than T(g,bulk) + 40 K, all probe molecules were mobile. In the range between 0 and 40 K above T(g,bulk) the fraction of mobile probe molecules strongly depends on film thickness. In 30-nm thin films mobility is observed at lower temperatures than in thick films. The fractions of mobile probe molecules were compared and rationalized using Monte Carlo random walk simulations. Results of these simulations indicate that the observed heterogeneities can be explained by a model which assumes a T(g) profile and an increased probability of probe molecules remaining at the surface, both effects caused by a density profile with decreasing polymer density at the polymer-air interface.

Three-coordinate complexes (bromo)[4-(2,2-dimethyl-1,3-dioxolan-4-yl)-phenyl](tri-tert-butyl-phosphine)palladium (1) and (bromo){4-[(tetrahydro-2H-pyran-2-yloxy)methyl]phenyl}(tri-tert-butyl-phosphine)palladium (2) were used to initiate Suzuki-Miyaura chain growth polymerization of 7'-bromo-9',9'-dioctyl-fluoren-2'-yl-4,4,5,5-tetramethyl-[1,3,2]dioxaborolane (3). The polymerization was optionally terminated by end-capping with red-emitting N-(2-ethylhexyl)-1,6-bis(4-tert-octylphenoxy)-9-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-perylene-3,4-dicarboximide. Heterodisubstituted polyfluorenes of adjustable molecular weights between 5 × 10(3) and 1.0 × 10(4) g mol(-1) and narrow molecular weight distribution (M(w)/M(n) < 1.2), bearing precisely one or two hydroxyl groups on one chain end and optionally a dye-label on the opposite end, were obtained virtually devoid of any side-products. Covalent attachment of polyethylene glycol (M(n) = 2 × 10(3) g mol(-1)) to the reactive end groups yielded amphiphilic block copolymer, which afforded stable nanoparticles with diameters in the range of 25-50 nm when dispersed in water. These particles exhibited a bright fluorescence emission with quantum yields as high as Φ = 84%, which could optionally be tuned to longer wavelengths by energy transfer to the perylene monoimide dye. The heterodifunctional nature of these polyfluorenes is crucial for a bright and enduring fluorescence brightness as revealed by comparison to nanoparticles containing physically mixed dye. Further addition of terrylene diimide dye to the nanoparticles of perylene-end-capped polyfluorene block copolymers allows for an energy cascade resulting in emission exclusively in the deep red and near-infrared regime.

In catalytic copolymerization, undesired chain transfer after incorporation of a polar vinyl monomer is a fundamental problem. We show an approach to overcome this problem by a fast consecutive insertion. The second double bond of acrylic anhydride rapidly inserts intramolecularly to regio- and stereoselectively form a cyclic repeat unit and a primary alkyl favorable for chain growth (>96%). This results in significantly enhanced copolymer molecular weights vs monofunctional acrylate monomers.

Translational diffusion of single perylene diimide molecules in 25 nm thin polymer films was investigated by single molecule widefield fluorescence microscopy. Spatial heterogeneities in single molecule motion were detected and analyzed by a new, quantitative method which draws a comparison of log-Gaussian fits of experimentally determined diffusion coefficient-distributions and diffusion coefficient-distributions from Monte Carlo random walk simulations. Heterogeneities could be observed close to the glass transition temperature, but disappear at ca. 1.1 × T(g). At higher temperatures, heterogeneities do not exist or they average out on the time and length scales of observation. The observed heterogeneities also explain why the dependency of diffusion coefficients on temperature does not follow Vogel-Fulcher-Tammann behavior.

Abstract

Polymer single crystals consisting of folded chains are always in a nonequilibrium state, even if they are faceted with a well-defined envelope reflecting the parameters of the crystal unit cell. Heterogeneities like small variations in the degree of chain folding within such crystals are responsible for a rather broad range in melting temperature. Consequently, upon annealing at a given temperature, some parts may be above and some below their respective melting temperatures, inducing a lamellar thickening process, which may vary locally. To emphasize such variations, controlled annealing experiments are performed at comparatively low temperatures and for long times. For single crystals of low-molecular-weight polyethylene, the formation of the well-known "Swiss-cheese"-like morphology with randomly distributed holes of varying sizes within the annealed single crystal is observed. However, for high-molecular-weight polyethylene, a regular pattern appeared upon annealing, characterized by branches of equal width that are oriented perpendicular to the crystal edge. All branches end at the nucleation site. Interestingly, the resulting pattern depends sensitively on both crystallization and annealing conditions. These thermally induced regular patterns within a single crystal are attributed to a stable crystalline framework formed within polyethylene single crystals in the course of growth.