Atactic, crystallizing polymer

Poly(vinyl acetate) is an atactic material and is amorphous. Whilst the structure of polyfvinyl alcohol) is also atactic the polymer exhibits crystallinity and has essentially the same crystal lattice as polyethylene. This is because the hydroxyl groups are small enough to fit into the lattice without disrupting it. 

Monomer addition under radical propagation conditions leads to mainly an atactic configuration. As a consequence, radical polymerisations of asymmetric vinyl polymers usually lead to amorphous materials. However, if the substituent is small enough to enter into the crystal cell, atactic vinyl polymers can crystallise (an example is poly(vinyl fluoride)). 

Most cases of radiation-induced polymerizations of crystalline monomers lead to atactic, noncrystallizable polymers. This occurs because of the density difference between the polymer and monomer crystal, which does not allow the monomer enough mobility to orientate sufficiently during the propagation step to produce a stereoregular polymer. 

Polymers that cannot crystallize usually have some irregularity in their structure. Examples include the atactic vinyl polymers and statistical copolymers. 

Syndiotactic polypropylene became commercially available about ten years ago with the advent of single-site catalysts. Unlike its atactic and isotactic counterparts, its manufacture presented serious challenges to polymer scientists and engineers. Even under the best conditions, its syndiotacticity rarely exceeds 75%, based on pentad sequences. It typically has both a lower melting point (approximately 138 °C relative to approximately 155 to 160 °C) and density (0.89 g/cm3 relative to 0.93 g/cm3) than isotactic polypropylene. Syndiotactic polypropylene crystallites have a much more complex structure than the isotactic form, which impedes its crystallization. Therefore, in general, the syndiotactic form of polypropylene crystallizes very slowly. 

Very active catalysts for the preparation of strictly alternating butadiene-propylene copolymers (BPR) consist of V0(0R)2C1/i-Bu Al (R = neopentyl). The CH3 side groups in BPR stiffen the polymer chain and were expected to promote the formation of strain-induced structures. The fact that we could not detect strain-induced crystallization is probably due to an atactic configuration of the propylene units. 

A comparison of the crystal structures, NMR and IR spectra of various Yb(ll) and calcium complexes demonstrated that they were strikingly similar, a reflection of the nearly identical radii of Ybz+ and Ca2+.25 Nevertheless, the dibenzylytterbium(ll) analog of 127 produces polystyrene of high syndiotacticity (r= 94.9%, rr= 90.0%), whereas 127 itself yields only atactic or slightly syndiotactic polymer. A difference in Yb-L and Ca-L bond strengths, despite their similar lengths, has been proposed as the source of the difference.315... 

An atactic polymer can crystallize, for instance the case of polyacrylonitrile, whose crystallizability has been explained on the basis of local conformations, which produce extended and straight chains.140... 

While the lamellar structures present in spherulites are similar to those present in polymer single crystals, the folding of chains in spherulites is less organized. Further, the structures that exist between these lamellar structures are generally occupied by amorphous structures including atactic chain segments, low molecular weight chains, and impurities. 

Polymer glasses are formed best when the macromolecular chains are irregular in structure (atactic, branched, crosslinked) so that crystallization is prevented. Regular (isotactic, syndiotactic unbranched) polymer chains form glasses only if they are cooled down so fast that crystallization is prevented such a quenching procedure freezes the material in the glassy state even if the polymer is able to crystallize. 

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