Melt spinning liquid crystalline polymers

Elongational behavior is induced in the entrance of the spinning hole and in the transition region from backhole to actual capillary. In practice hardly any permanent orientation is built up in this way, however, because molecular relaxation is rapid. Spinning hole profiles are smoothened only to prevent the formation of vortices which would lead to extrudate distortion. Promoting orientation already in the spinning holes is not common for melt spinning. It could be beneficial for the orientation of melt-spun liquid-crystalline polymers, however, for example in the production of carbon fiber from pitch. 

The negative first normal stress difference under a medium shear rate, characterized by liquid crystalline polymers, makes the material avoid the Barus effect—a typical property of conventional polymer melt or concentrated solution, i.e., when a polymer spins out from a hole, or capillary, or slit, their diameter or thickness will be greater than the mold size. The liquid crystalline polymers with the spin expansion effect have an advantage in material processing. This phenomenon is verified by the Ericksen-Leslie theory. On the contrary, the first normal stress difference for the normal polymers is always positive. 

Ternary blends from a thermotropic liquid crystalline polymer, PEN, and PET were prepared by melt blending and melt spinning to fibers. The mechanical properties of ternary blend fibers could be significantly improved by annealing at 180°C for 2 h. This is attributed to the development of more ordered crystallites and to the formation of more perfect crystalline structures. The interfacial adhesion between PEN and liquid crystalline polymer phases is enhanced when the blends are processed with dibutyl-tindilaurate as a reactive catalyst to promote transesterification. 

There have been many attempts to change the melt flow properties of a polymer by incorporating a small amount of an anisotropic or an immiscible polymer. For example, Brody [220,221] demonstrated a windup speed up to 5000 m/min by adding a small amount of copoly(chloro-l,4-phenylene ethylene dioxy-4,4 -dibenzoate/terephthalate) (CLOTH) or copoly(4-hydroxybenzoic/6-hydroxy-2-naphthoic acid) into nylon-6,6. More recently, Vassi-latos [222] disclosed the melt spinning of nylon-6,6 at speeds up to 6000 m/min with the addition of a minor amount of liquid crystalline polymers such as CLOTH. This technique clearly offsets some of the cost advantages of high-speed spinning. 

In 1972, Cottis and coworkers at Carborundum patented wholly aromatic polyesters based on p-hydroxybenzoic acid (HBA), A,A -dihydrox-ybiphenyl (DHB), and terephthalic acid (TPA), one of which was later commercialized as EKKCEL 1-2000 [1]. In 1974, Kuhfuss and coworkers at Eastman Kodak reported a new polyester based on HBA and polyfethylene terephthalate) (PET), which was later marketed under the code of X-7G. X-7G is the first thermotropic liquid crystalline polymer to be fabricated by injection molding or melt spinning [2]. However, then Eastman Kodak withdrew its plan of marketing of X-7G and changed the target with a wholly aromatic polyester commercialized as TITAN (THERMX ) in 1996. As described later, it was acquired by DuPont in 2003. 

The question of how to spin a lyotropic liquid crystalline polymer which has high thermal stability and degrades before it melts presented a major challenge. Fortunately for the makers of PBO this question had already been answered during the development of Kevlar. PBO is spun directly from the PPA solution used... 

Lyotropic liquid crystalline polymers can be sprm into fibers by using a wet or gel spinning process, while thermotropic Uqrrid crystalline polymers can be made into fibers by melt spinning. Although both lyotropic and thermotropic liquid crystalline polymers can be made into fibers, most successful liqrrid crystal fibers are based on lyotropic polymers. One such example is polyphertylene terephthalamide (PPTA, Kevlar ), which was first produced by DuPont in 1972. 

For lyotropic liquid crystalline polymers, either wet-spinning or dry-jet-wet spinning are employed to produce fibers. A lyotropic state of a polymer solution is formed at a specified concentration and temperatnre in a nonvolatile solvent. The anisotropic polymer solution is extruded into a non-solvent bath, where fiber coagulation and solvent extraction take place. For thermotropic liquid crystalline polymers, a melt spuming method is applied. 

The melt-spinning process used to convert mesophase pitch into fiber form is similar to that employed for many thermoplastic polymers. Normally, an extruder melts the pitch and pumps it into the spin pack. Typically, the molten pitch is filtered before being extruded through a multi-holed spinnerette. The pitch is subjected to high extensional and shear stresses as it approaches and flows through the spinnerette capillaries. The associated torques tend to orient the liquid crystalline pitch in a regular transverse pattern. Upon emerging from the... 

It was, however, observed that such systems under appropriate conditions of concentration, solvent, molecular weight, temperature, etc. form a liquid crystalline solution. Perhaps a little digression is in order here to say a few words about liquid crystals. A liquid crystal has a structure intermediate between a three-dimensionally ordered crystal and a disordered isotropic liquid. There are two main classes of liquid crystals lyotropic and thermotropic. Lyotropic liquid crystals are obtained from low viscosity polymer solutions in a critical concentration range while thermotropic liquid crystals are obtained from polymer melts where a low viscosity phase forms over a certain temperature range. Aromatic polyamides and aramid type fibers are lyotropic liquid crystal polymers. These polymers have a melting point that is high and close to their decomposition temperature. One must therefore spin these from a solution in an appropriate solvent such as sulfuric acid. Aromatic polyesters, on the other hand, are thermotropic liquid crystal polymers. These can be injection molded, extruded or melt spun. 

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