Chapter 3

Molecular Engineering of Liquid Crystalline Polymers

3.1.

INTRODUCTION

The molecular theories introduced in Chapter 2 are the principal guidelines for any successful molecular design of liquid crystalline polymers. According to the theories, rigid molecules with an anisotropic shape, rod-like in particular, are able to form nematic phases even if no soft interactions are included in the consideration. Thermal stability (characterizable by Ti , the clearing temperature) of the liquid crystal phase is a function of the axial ratio of the molecules. Those molecules with higher length-to-diameter ratios will result in nematic phases of a higher clearing temperature. When the ratio is large enough, the nematic phase is always more stable than the isotropic liquid phase and the clearing temperature will be innite. Dierent theoretical treatments have reached the same conclusion, although they have resulted in dierent critical axial ratios. In the literature of polymeric liquid crystals, the most cited value for the critical axial ratio of rigid rods is 6.4, given by Flory. Actual molecules always have certain exible elements and are not as rigid as a true rod. Taking the rod-like poly(1,4-phenylene) as one example,

3.1
n

rotation of phenylene rings about the interphenylene bonds, together with vibrations of the bonds, have brought about exibility of the molecule even
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though a rod-like shape has persisted. The formability of a liquid crystal phase and the phase transition temperatures of the homologous compounds of poly(1,4-phenylene) are characterized and shown in Table 3.1. Two conclusions may be drawn from the data in Table 3.1. First, only the homologues with suciently large values of length-to-diameter ratio can form a liquid crystal phase. Secondly, both the melting point and the clearing temperature of the liquid crystal phase increase very fast with an increasing degree of polymerization (n + 2). The compound with only six 1,4-phenylene units and an axial ratio of 5.5 has a melting point of 438 C and a clearing temperature of 565 C, which is already too high a temperature for organic molecules to survive. It is therefore not practical to synthesize liquid crystal forming polymers by the simple linking-together of rigid structures into rod-like molecules, even if certain exible elements are present. By inserting in between every two phenylene rings a linking unit with a certain exibility, such as an ester group, the exibility of the molecules will be increased. For example, if an ester group is used as the linking unit, it will not only allow the crankshaft type movements in the molecule, but also serve as a separation between the phenylene rings and thus reduce the hindrance for a free rotation of the rings. As a result, poly(4-hydroxybenzoic acid), PHA, with the following formula does have much lower transition temperatures than poly-phenylenes as shown in Table 3.2. Specically, the compound with n = 3 has a melting point of 220 C and a clearing temperature of 464 C. The calculated axial ratio l/d is 6.4. In comparison, this compound has slightly higher axial ratio but much lower transition temperatures than the poly(1,4-phenylene) with n + 2 = 6 (l/d = 5.5, m.p.

Table 3.1. The Axial ratio and Phase Transition Temperature of Poly(1,4-phenylene)s . n+2 1 2 3 4 5 6

Axial Ratio, l/d 1.0 2.0 3.0 3.9 4.8 5.5

Melt. Point, C 5.4 70.5 213 320 388 438

Clearing Point, C non-liquid-crystalline non-liquid-crystalline non-liquid-crystalline non-liquid-crystalline 418 565

Source: Irvine and Flory, 1984.

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Table 3.2. Axial ratio hydroxybenzoic acid) . n 1 2 3 13 100

and

Transition

Temperature

of

Poly(4-

Axial Ratio, l/d 3.8 5.1 6.4 19

Melt.Point, C 132 176 220 415 600

Clearing Point, C 100 monotropic 254 464

Source: Ballau and Flory, 1984; Economy, et al. 1988.

438 C, T i = 565 C. Table 3.1). Thus, PHA can have a higher degree of polymerization than poly(1,4-phenylene) before the transition temperatures become innite. However, studies on PHA have shown that its melting point is already higher than its decomposition temperature if the degree of polymerization reaches only such a low value as 13 (Table 3.2).
CO O CO n O

3.2

In Table 3.2, the compound with n = 1 has a monotropic liquid crystalline phase. In the literature of liquid crystals a monotropic phase is a metastable phase which forms only in the process of cooling but not when the sample is heating. On the other hand, if a liquid crystalline phase forms not only in the process of cooling but also in the process of heating, the phase is termed enantiotropic. For example, a nematic phase is monotropic if the melting point, T m, of the sample is higher than the clearing temperature, T i, of the liquid crystal phase. It is enantiotropic if T i is higher than T m. It is worthwhile pointing out that the critical axial ratio 6.4 given by Florys theory is based on assumptions that include zero free volume and zero net interaction energy between the rods (Chapter 2). By increasing the free volume, for example, the ratio will be increased accordingly. It is thus also understandable that the critical axial ratio will become larger when the temperature is increased. On the other hand, no actual system will meet these assumptions to any perfection. In addition, the exibility of an actual molecule such as poly(1,4-phenylene) and PHA will increase with increasing temperature. In other words, the axial ratio of a molecule is not a constant,

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but a function of temperature. The actual axial value of a compound will deviate from what was calculated for a standard condition, and will become lower and lower with the increase of experimental temperature. Therefore, no direct comparison may be made between the critical axial ratio given by the theory and the axial ratio of an actual compound for evaluation of the liquid crystalline properties of the compound. We have shown that polymers formed by the simple linking together of rigid rod-like mesogenic units, such as poly(1,4-phenylene) and poly(4hydroxybenzoic acid) formed by linking together the phenylene rings with single bonds or ester units, have melting temperatures so high that no liquid crystalline phase can actually exist above melting. To achieve liquid crystallinity, the melting point of the polymers has to be decreased. The most convenient way to achieve this is to mix the rod-like polymer with a solvent. Blades (1973, 1975) discovered that with sulfuric acid the high molecular weight poly(1,4-phenylene terephthamide) is able to form crystalline solvates with nite melting temperatures. The solvate formed with about one mole polymer and 10 moles of sulfuric acid melts and forms the lyotropic liquid crystalline phase at 70 C, a very convenient temperature for processing. Other rod-like polymers may form solvates also. Poly( -benzyL-glutamate), for example, forms crystal solvates with DMF. Watanabe et al. (1981) found the melting point of the solvates increases with the increasing of the polymer content. The lyotropic liquid crystal phase can form only when the polymer content is higher than 18 wt%. Papkov (1982) has given a phase diagram for the two-component system of a rigid rod polymer and a solvent. According to this researcher, with the addition of a solvent to the polymer, a two-phase system (crystal C + crystal-solvate CS) is rst formed. A single CS phase, then the second two-phase system of CS and the isotropic liquid phase will form with the further addition of the solvent. Thus in principle, liquid crystals of rigid rod-like polymers can be obtained by solvent incorporation and formation of crystal solvates with nite melting points. As a matter of fact, lyotropic liquid crystal phases are achieved not only with poly(1,4-phenylene terephthamide) (PPTA) and Poly( -benzy-L-glutamate), but also with such rigid rod-like polymers as poly(1,4-phenylene benzo-bis-thiazole) (PBT) and poly(1,4phenylene benzo-bis-oxazole) (PBO). PPTA, PBT and PBO are important lyotropic liquid crystal polymers that result in materials with very high tensile strength and modulus. Unfortunately, because of the very low mixing entropy, not many of the rigid rod-like high polymers have sucient solubility and form solvates. For example, among many others, poly(1,4-phenylene) and

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poly(4-hydroxybenzoic acid) hardly dissolve in any solvent. Therefore, these high-melting polymers are not able to form any liquid crystalline phase, neither thermotropic nor lyotropic, if no substantial chemical modications of the molecules are made. It has been indeed the focus of molecular engineering in this scientic area to design and synthesize polymers with desirable liquid crystallinity in desirable temperature regions. To achieve the goal, two principal ideas have been developed. The rst is to disrupt the chain sequence of mesogenic units by inserting into the chain, dierent structural moieties, so as to incorporate in the chain certain irregularity and exibility. The result of this practice are main-chain type liquid crystalline polymers. The second idea is to use the mesogenic units individually as side groups attached to the main chain of the polymer molecules, resulting in side-group type liquid crystalline polymers. Depending on the extent of disruption in the sequence of mesogenic units, main-chain type liquid crystalline polymers of very dierent properties can be synthesized. The polymers can still be rather rigid and have very high, but acceptable melting temperatures if only rigid moieties are used as the disruptions. Copolyesters of 4-hydroxybenzoic acid (HBA) with 6-hydroxy-2-naphthalic acid (HNA), and copolyesters of HBA with terephthalic acid (TA) and biphenol, are famous examples of these polymers. Properties of these copolyesters will be further discussed in Section 3.3 and Chapter 5. On the other hand, main-chain type liquid crystalline polymers can be very exible with very low melting points if exible spacers are frequently incorporated along the chain. By comparison, side-group type liquid crystalline polymers usually are exible polymers with low T g or low melting temperatures because the rigid mesogenic units with only limited length-to-diameter ratio are used only as individual side groups (Section 3.4). However, side-group type liquid crystalline polymers can have properties similar to that of rigid or semi-rigid main-chain type liquid crystalline polymers if unusual molecular designs are adopted (Section 3.5). Naturally, dierent molecular designs result in dierent polymer properties and dierent applications. Liquid crystalline polymers with higher chain rigidity and melting points may nd applications as high-strength, high-modulus, and heat-resistant materials (Chapter 5). Those with very low chain rigidity and transition temperatures may be used in display or information process devices (Chapter 6). Liquid crystalline polymers have been classied in a variety of ways according to the style of incorporation of mesogenic units in the molecules. The most basic types are shown in Figure 3.1, in which the squares are representative of mesogenic units. Mesogenic units are structural moieties with sucient rigidity and are mostly in the shape of straight rods. Other

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Figure 3.1.

Basic types of liquid crystalline polymers.

anisotropic shapes such as discotic and bowl-like ones are rare but can also be found in certain liquid crystalline polymers. It is commonly believed that mesogenic units are essential to the formation of the liquid crystal phase. Liquid crystalline polymers without mesogenic units are rare and will be discussed in Section 3.6. 3.2. LOW MASS LIQUID CRYSTALLINE COMPOUNDS AND MESOGENIC UNITS

By and large, mesogenic units make up most of the principal components in a liquid crystalline polymer. The structure and property of mesogenic units are of primary importance in determining properties of a polymer. It is thus very instructive to have a brief study of the structure and its inuence on the property of mesogenic units with low mass liquid crystalline compounds as models and references.