The stereosequence distribution of the “atactic” and “isotactic” fractions of a polypropylene
sample made with a MgCl2-supported catalyst was determined by means of high-resolution 13C NMR
and analyzed in terms of statistical models of increasing sophistication. Two-site models, including the
one normally used for the interpretation of “routine” 13C NMR data at pentad level, were shown to be
inconsistent with the much finer high-resolution data. A good agreement between experimental and
calculated distributions could be obtained only in terms of a three-site model, describing each fraction as
a mixture of highly isotactic, weakly isotactic (“isotactoid”) and syndiotactic sequences. According to such
model, the two fractions comprise the same three building blocks (the configuration of the three different
types of stereosequences being almost invariant) and differ merely in their relative amounts (which
indicates a stereoblock nature). The correlations with the physical properties of the materials and the
implications on the nature of the catalytic species are also briefly discussed.
Unprecedented rhodium-catalyzed stereoselective polymerization of "carbenes" from ethyl diazoacetate (EDA) to give high molecular mass poly(ethyl 2-ylidene-acetate) is described. The mononuclear, neutral [(N,O-ligand)M(I)(cod)] (M = Rh, Ir) catalytic precursors for this reaction are characterized by (among others) single-crystal X-ray diffraction. These species mediate formation of a new type of polymers from EDA: carbon-chain polymers functionalized with a polar substituent at each carbon of the polymer backbone. The polymers are obtained as white powders with surprisingly sharp NMR resonances. Solution and solid state NMR data for these new polymers reveal a highly stereoregular polymer, with a high degree of crystallinity. The polymer is likely syndiotactic. Material properties are very different from those of atactic poly(diethyl fumarate) polymer obtained by radical polymerization of diethyl fumarate. Other diazoacetates are also polymerized. Further studies are underway to reveal possible applications of these new materials.
The results of realistic computer simulations of dense polymer melts filled with solid nanoparticles are compared with results obtained for similar systems near planar solid surfaces and with those of Monte Carlo calculations performed for single chains in the presence of spherical solid obstacles. The polymer units at the interface with the filler particles are arranged in densely packed and ordered shells analogous to those found near planar solid surfaces. The polymer chains, reduced in size compared to the unfilled melt, are constituted of sequences of surface segments, totally contained in the interface shell of a given particle, and of bridge segments, connecting different particles. Each chain visits the interface shell of several filler particles, and each particle is in contact with many different polymer chains, such that the filler particles behave as highly functional physical cross-links.
In this paper, we present the results of Monte Carlo simulations of the static properties of polymer melts confined between hard walls. The simulations are conducted in the canonical ensemble with a method that is a combination of reptation and crankshaft motions. 1250 polymer chains each comprising of 100 connected beads are placed in a box which allows for the simulation of a typical polymer melt confined between two hard plates at a separation of 51 bead diameters. Noncovalently bonded beads are assumed to interact with an empirical 6-12 Lennard-Jones potential which has parameters chosen to simulate a polyethylene melt at 400 K. From the analysis of the simulation results we show the existence of two relevant length scales in the problem. Single-chain statistics are perturbed by the wall, and this effect is screened out only after one proceeds to a distance comparable to twice the unperturbed radius of gyration of the polymer chain. However, many-chain statistics, i.e., packing and orientation of chain segments, are screened out as soon as one proceeds about three times the bead size from the wall. The simulation also allows for the study of the conformations of chains near the wall, and we observe that chains near the surface are flattened into nearly two-dimensional structures. The interface therefore corresponds to a region where chain configurations gradually evolve from this nearly two-dimensional structure to the unperturbed, three-dimensional Gaussian configurations in the bulk.
13C NMR spectroscopy is the main source of information
on the stereochemistry of Ziegler−Natta and related transition metal catalyzed propene polymerizations.
In simple cases, like those of
polypropylenes formed under pure enantiomorphic-site or chain-end
control, the origin of the stereoselectivity can be easily recognized from the steric pentad distribution
obtained from routine 13C NMR
spectra. On the other hand, the variety of innovative polymers
that can now be prepared with “high-yield” heterogeneous and metallocene-based homogeneous catalysts under
hybrid, multiple, or oscillating
stereocontrol represent very complex systems, which are beyond the
possibilities of configurational analysis
by routine 13C NMR. In such cases, high-field
13C NMR can be highly advantageous. Indeed, in
this
paper we show that from the methyl and methylene regions of 150 MHz
13C NMR spectra of polypropylenes
of various tacticities, the stereosequence distribution can be
determined at a much finer level of detail,
so as to obtain an adequate experimental basis for the investigation of
the many complicated mechanisms
of stereocontrol presently encountered in Ziegler−Natta
catalysis.
124 ± Io in all conformations after energy minimization. The interdiad bond angle = 106°when both adjoining skeletal bonds are trans t, « 1110 when one bond is t and the other g or g, and = 116°when both are g or g. The spatial configurations found to be of lowest energy for stereoregular chains are in excellent agreement with crystallographic studies on i-PMMA and with results of wide-angle X-ray scattering of s-PMMA. The backbone torsional angles for the various energy minima can be represented approximately by six discrete states that form the basis for a rotational isomeric state treatment. Conformations near trans are preferred; the preference is pronounced for s-PMMA. Characteristic ratios and their temperature coefficients calculated according to the six-state scheme are in satisfactory agreement with experimental results. Parameters used in these calculations follow directly from the conformational energy calculations; adjustments are not required.
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