Crystallinity, reversal

Jeong H.M., Ahn B. and Kim B.K. (2000), Temperature sensitive water vapour permeability and shape memory effect of polyurethane with crystalline reversible phase and hydrophilic segments. Polymer International, 49 pp. 1714-1721. 

The C-C linkage in tire polymeric [60]fullerene composite is highly unstable and, in turn, tire reversible [2+2] phototransfonnation leads to an almost quantitative recovery of tire crystalline fullerene. In contrast tire similarly conducted illumination of [70]fullerene films results in an irreversible and randomly occurring photodimerization. The important aspect which underlines tire markedly different reactivity of tire [60]fullerene polymer material relative to, for example, tire analogous [36]fullerene composites, is tire reversible transfomration of tire fomrer back to the initial fee phase. 

Assemble in a fume-cupboard the apparatus shown in Fig. 67(A). Place 15 g. of 3,5-dinitrobenzoic acid and 17 g. of phosphorus pentachloride in the flask C, and heat the mixture in an oil-bath for hours. Then reverse the condenser as shown in Fig. 67(B), but replace the calcium chloride tube by a tube leading to a water-pump, the neck of the reaction-flask C being closed with a rubber stopper. Now distil off the phosphorus oxychloride under reduced pressure by heating the flask C in an oil-bath initially at 25-30, increasing this temperature ultimately to 110°. Then cool the flask, when the crude 3,5-dinitro-benzoyl chloride will solidify to a brown crystalline mass. Yield, 16 g., i.e,y almost theoretical. Recrystallise from caibon tetrachloride. The chloride is obtained as colourless crystals, m.p. 66-68°, Yield, 13 g Further recrystallisation of small quantities can be performed using petrol (b.p. 40-60°). The chloride is stable almost indefinitely if kept in a calcium chloride desiccator. 

No polymer is ever 100% crystalline at best, patches of crystallinity are present in an otherwise amorphous matrix. In some ways, the presence of these domains of crystallinity is equivalent to cross-links, since different chains loop in and out of the same crystal. Although there are similarities in the mechanical behavior of chemically cross-linked and partially crystalline polymers, a significant difference is that the former are irreversibly bonded while the latter are reversible through changes of temperature. Materials in which chemical cross-linking is responsible for the mechanical properties are called thermosetting those in which this kind of physical cross-linking operates, thermoplastic. 

In the last three chapters we have examined the mechanical properties of bulk polymers. Although the structure of individual molecules has not been our primary concern, we have sought to understand the influence of molecular properties on the mechanical behavior of polymeric materials. We have seen, for example, how the viscosity of a liquid polymer depends on the substituents along the chain backbone, how the elasticity depends on crosslinking, and how the crystallinity depends on the stereoregularity of the polymer. In the preceding chapters we took the existence of these polymers for granted and focused attention on their bulk behavior. In the next three chapters these priorities are reversed Our main concern is some of the reactions which produce polymers and the structures of the products formed. 

Secondary amines give only a monosubstituted product. Both of these reactions are thermally reversible. The product with ammonia (3,3, 3 -nitrilottispropionamide [2664-61-1C H gN O ) (5) is frequently found in crystalline acrylamide as a minor impurity and affects the free-radical polymerisation. An extensive study (8) has determined the stmctural requirements of the amines to form thermally reversible products. Unsymmetrical dialkyl hydrasines add through the unsubstituted nitrogen in basic medium and through the substituted nitrogen in acidic medium (9)). 

At very low concentrations of water, or in foods held below the free2ing point of water, physical conditions may be such that the available water may not be free to react. Under these conditions, the water may be physically immobi1i2ed as a glassy or plastic material or it may be bound to proteins (qv) and carbohydrates (qv). The water may diffuse with difficulty and thus may inhibit the diffusion of solutes. Changes in the stmcture of carbohydrates and proteins from amorphous to crystalline forms, or the reverse, that result from water migration or diffusion, may take place only very slowly. 

Tripolyphosphates. The most commercially important tripolyphosphate salt is sodium tripolyphosphate (STP), Na P O Q. Three distinct crystalline forms are known two are anhydrous (STP-I and STP-II) the other is the hexahydrate [15091 -98-2] Na P O Q 6H20. Sodium tripolyphosphate anhydrous Form I is the high temperature, thermodynamically stable phase sodium tripolyphosphate anhydrous Form II is the lower temperature form which can be readily converted to STP-I by heating to above 417 8° C, the transition temperature. However, the reverse reaction is extremely slow below 417°C. Both anhydrous forms of sodium tripolyphosphate are therefore stable enough to coexist at room temperature. 

Ammonium chloride [12125-02-9] NH Q, ammonium bromide [12124-97-9] NH Br, and ammonium iodide [12027-06-4] NH I, are crystalline, ionic compounds of formula wts 53.49, 97.94, and 144.94, respectively. Their densities d systematically foUow the increase in formula weight 1.53, 2.40, and 2.52. AH three exist in two crystal modifications (10) the chloride, bromide, and iodide have the CsQ stmcture below temperatures of 184.5, 137.8, and — 17.6°C, respectively each reversibly transforms to the NaQ. stmcture at higher temperatures. 

GVD Coatings. As in PVD, the stmcture of the deposited material depends on the temperature and supersaturation, roughly as pictured in Figure 8 (12). In the case of CVD, however, the effective supersaturation, ie, the local effective concentration in the gas phase of the materials to be deposited, relative to its equiUbrium concentration, depends not only on concentration, but on temperature. The reaction is thermally activated. Because the effective supersaturation for thermally activated reactions increases with temperature, the opposing tendencies can lead in some cases to a reversal of the sequence of crystalline forms Hsted in Figure 8, as temperature is increased (12). 

Crystallization. Raw natural mbber may freeze or crystallize during transit or prolonged storage, particularly at subzero temperatures. The mbber then becomes hard, inelastic, and usually much paler in color. This phenomenon is reversible and must be differentiated from storage hardening. The rate of crystallization is temperature-dependent and is most rapid at —26° C. Once at this temperature, natural mbber attains its maximum crystallinity within hours, and this maximum is no more than 30% of the total mbber. 

The pseudocross-links, generated by the hard-segment interactions, are reversed by heating or dissolution. Without the domain crystallinity, thermoplastic polyurethanes would lack elastic character and be more gum-like in nature. In view of the outlined morphology, it is not surprising that many products develop their ultimate properties only on curing at elevated temperature, which allows the soft- and hard-phase segments to separate. 

Photochromism Based on Redox Reactions. Although the exact mechanism of the reversible electron transfer is often not defined, several viologen salts (pyridinium ions) exhibit a photochromic response to uv radiation in the crystalline state or in a polar polymeric matrix, for example,... 

---