Macromolecular crystallinity

Macromolecular crystallinity differs in three important ways from low-molecular weight molecular crystallinity polymers never crystallize completely, the unit cells are always smaller than the macromolecule, i.e. the crystal lattice is formed by the subunits rather than by the whole molecule and a long polymer chain can thread through different crystallites. Complete crystallization is impeded because of the structural polydispersity and the topological constraints resulting from the fact that... 

Intercalation compounds - Compounds resulting from reversible inclusion, without covalent bonding, of one kind of molecule in a solid matrix of another compound, which has a laminar structure. The host compound, a solid, may be macromolecular, crystalline, or amorphous. [5]... 

An interesting application of this reaction was the use of macro-molecular anhydrides, namely, styrene-maleic anhydride or vinyl acetate-maleic anhydride copolymers in the presence of perchloric acid as catalyst, these copolymers acylate mesityl oxide or d rpnone to macromolecular pyrylium salts which, with aryl substituents, are fluorescent.No crystalline products could be obtained from succinic anhydride because of the solubility and ease of decarboxylation. 

Within the class of polymer crystals having, ideally, long-range positional order for all the atoms, different crystalline forms (polymorphs) may arise as a result of having different almost isoenergetic macromolecular conformations (of the main chain, in most known cases) or as a result of different, almost isoenergetic modes of packing of macromolecules with identical conformations [1-3]. 

Ionic LCs are interesting systems because they combine the properties of LCs with those of ionic liquids. Although alkali metal soaps were among the first thermotropic LCs to be systematically studied, ionic liquid crystalline derivatives have been reported less frequently than those based on neutral molecular and macromolecular species [39]. When the halide of [AuX(CNR)] complexes is substituted by a second isocyanide, ionic complexes [Au(CNR)2][Y] [R = C6H40C H2 + i (27a),... 

This is not equally valid for macromolecular compounds, in which a molecule consists of a nearly unlimited number of atoms. The interactions with surrounding molecules cannot be neglected in this case. For instance, for a substance consisting of thread-like macromolecules, it makes a difference to the physical properties whether the molecules are ordered in a crystalline manner or whether they are tangled. 

In the laboratories of Natta in Milan it was found that the Ziegler catalysts could polymerize (besides ethene) propene, styrene, and several a-olefins to high linear polymers. These polymers appeared crystalline when examined by X-ray diffraction techniques and were able to give oriented fibers. In less than one year since the preparation of the first polymer of propene, Natta was able to communicate, in the meeting of the Accademia dei Lincei of December 1954 in Rome, that a new chapter had been disclosed in the field of macromolecular chemistry, due to the discovery of processes to obtain polymers with an extraordinary regularity in their structure in terms of both chemical constitution and configuration of the successive monomeric units along the chain of each macromolecule. 

Preparation of X-ray amorphous ZSM-5 crystallites according to procedure BT It is important that the gel formation takes place as homogeneously as possible. Because of the particular sensitivity of various silica and alumina species to the pH (63,64), the pH range between 4.5 and 8.5 was avoided. Nucleation was performed at pH 3.5-4, where a low viscous gel containing essentially monomeric silica species is rapidly formed (65).The, pH is theii raised to about 9, in order to form tetrahedral A1(0H) entities and to favour the further A1 incorporation within the zeolitic framework. NaCl was used to increase the (super)saturation of the gel, which will flocculate into a macromolecular colloid (V) and initiate the nucleation. This procedure yields 100 % crystalline zeolite after... 

These traps, (Fig. 6) and similar effects in the motion of holes and other charges through polymers, would eventually be correlated also with such structural probes as positron lifetimes in macromolecular solids. Extensive recent studies of positron lifetime are based on positronium decay. In this, the lifetime of o-positronium (bound positron-electron pair with total spin one) is reduced from about 140 nanoseconds to a few nanoseconds by "pick-off annihilation" in which some unpaired electron spins in the medium cause conversion quenching of orthopositronium to para-positronium. The speed of the t2 effect is supposed, among other things, to represent by pick-off annihilation the presence of defects in the crystalline lattice. In any case, what amounts to empty space between molecules can then be occupied by orthopositronium.(14,15,16) It is now found in linear polyethylene, by T. T. Wang and his co-workers of Bell Laboratories(17) that there is marked shift in positron lifetimes over the temperature range of 80°K to 300°K. For... 

---