Crystalline macromolecules, melting

Vandenberg, E.J. Tian, D. A new, crystalline high melting bis(hydroxymethyl)- polycarbonate and its acetone ketal for biomaterial applications. Macromolecules 1999, 32 (11), 3613-3619. 

Boyle F. P., Taylor, P. L., Hopflnger, A. J., Simha, R., Hybrid Ising mean field theories of crystalline polymer melt processes. Macromolecules, 9(4), pp. 599-603 (1976). 

The zero shear viscosity scales with Nf" to contrast Af dependence for isotropic polymers [20] So far, we have examined the dynamics of rod-Uke macromolecules in isotropic semi-dilute solution. For anisotropic LCP solutions in which the rods are oriented in a certain direction, the diffusion constant increases, and the viscosity decreases, but their scaling behavior with the molecular weight is expected to be unchanged [2,17], Little experimental work has been reported on this subject. The dynamics of thermotropic liquid crystalline polymer melts may be considered as a special case of the concentrated solution with no solvent. Many experimental results [16-18] showed the strong molecular weight dependence of the melt viscosity as predicted by the Doi-Edwards theory. However, the complex rheological behaviors of TLCPs have not been well theorized. 

Two approaches to the attainment of the oriented states of polymer solutions and melts can be distinguished. The first one consists in the orientational crystallization of flexible-chain polymers based on the fixation by subsequent crystallization of the chains obtained as a result of melt extension. This procedure ensures the formation of a highly oriented supramolecular structure in the crystallized material. The second approach is based on the use of solutions of rigid-chain polymers in which the transition to the liquid crystalline state occurs, due to a high anisometry of the macromolecules. This state is characterized by high one-dimensional chain orientation and, as a result, by the anisotropy of the main physical properties of the material. Only slight extensions are required to obtain highly oriented films and fibers from such solutions. 

Free radical vinyl polymerization, the oldest process, leads to branched low density polyethylene (LDPE). Macromolecules have numerous short branches, which reduce the melting point, tensile strength and crystallinity. Polymers are relatively flexible because of the high volume of the branched molecule and the low crystallinity. 

LCP phases are subdivided into thermotropic or lyotropic. Lyotropic liquid crystals are formed by macromolecules that show liquid crystalline behavior in solution. This behavior is strongly concentration dependent. Thermotropic liquid crystals are molecules that show liquid crystalline behavior above the melting point of their crystallites. 

The prediction of the chemical thermostability is based on the rules on the thermal stability and the reactivity of chemical bonds known for low-molecular-weight compounds. Instead, the physical thermostability depends on the transition points of the macromolecules, i.e., the glass transition temperature Tg in case of amorphous polymers, and additionally the crystalline melting point in case of crystalline polymers. 

Thermal Properties. A typical dsc thermogram of an HPL/PVA blend (Fig. 4) shows a single Tg and Tm (10). Differences in the shape of the melting endotherms of PVA(96), (88), and (75) can be attributed to different degrees of crystallinity in the three polymers. Changes in crystalline structure of polymer blends usually result from polymer-polymer interactions in the amorphous phase. Such interactions result in a reduction of crystallinity, thereby reducing the enthalphy of the phase change (16,17). The observed reductions in melt endotherm area of HPL blends with PVA (> 0) may therefore indicate the existence of polymer-polymer interactions between the two types of macromolecules. 

Isotactic poly(x-olcfin)s crystallise in a helical conformation, and, in the case of polypropylene, with three units per turn [4,5], Isotactic polypropylene has a melting point of 175°C and does not dissolve in boiling n-heptane [6,7], Note that, depending upon the configuration of the tertiary carbon atom of the polymer main chains, the poly(x-olefin) helices will be characterised by right-handedness or left-handedness. It should be mentioned that the helical structure of the poly(x-olcfin) chain per se is sufficient for the appearance of chirality of such a macromolecule [8], Figure 3.3 presents the helical conformation of chains of isotactic poly(a-olefin)s in the crystalline state (with three units per turn - the case of polypropylene) [5],... 

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