Main chains, SCLCP

In general terms, high molar mass liquid crystals are classified according to the location of the mesogenic unit in the polymer. Thus, they are either incorporated into the main chain (main-chain liquid crystal polymers - MCLCP Fig. 5A) or they are pendant from the main chain (side-chain liquid crystal polymers - SCLCP Fig. 5B). 

All Liquid Crystal Polymers are characterised by the fact that they contain stiff meso-genic groups, often inserted in flexible chain systems (so called "spacers") and connected to them by linking functional groups the mesogenic unit is inserted either in the main chain or in the side chains or (in exceptional cases) in both. We shall discuss MCLCPs and SCLCPs. A schematic representation of common structures of LCPs is displayed in Fig. 6.14 (Jansen, 1996). An example of a SCLCP with disc-like mesogens is displayed in Fig. 6.15 (Franse et al., 2002, 2004). 

ROMP Ring-opening metathesis polymerization ADMET Acyclic diene metathesis polymerization ALTMET Alternating diene metathesis polycondensation MCLCP Main chain liquid crystalline polymer SCLCP Side chain liquid crystalline polymer mru molecular repeating unit... 

Liquid crystallinity can be attained in polymers of various polymer architectures, allowing the chemist to combine properties of macromolecules with the anisotropic properties of LC-phases. Mesogenic imits can be introduced into a polymer chain in different ways, as outhned in Fig. 1. For thermotropic LC systems, the LC-active units can be connected directly to each other in a condensation-type polymer to form the main chain ( main chain liquid crystalline polymers , MCLCPs) or they can be attached to the main chain as side chains ( side chain liquid crystalline polymers , SCLCPs). Calamitic (rod-Uke) as well as discotic mesogens have successfully been incorporated into polymers. Lyotropic LC-systems can also be formed by macromolecides. Amphiphihc block copolymers show this behavior when they have well-defined block structures with narrow molecular weight distributions. 

SCLCPs combine liquid crystalline properties and polymeric behavior in one material. If the mesogenic unit is fixed directly to the polymer main chain, the motion of the liquid crystalline side chain is coupled with the motion of the polymer backbone, preventing the formation of a LC mesophase. Therefore, Finkelmann and Ringsdorf proposed that the introduction of a flexible spacer between the main chain and the mesogenic unit would decouple their motions, allowing the mesogenic moiety to build up an orientational order [29,30]. 

Cho et al. described the synthesis and polymerization of 4,8-cyclododeca-dien-l-yl-(4 -methoxy-4-biphenyl) terephthalate VIII [54,55]. Polymerization was carried out with WCl4(OAr)2/PbEt4. The double bonds in the polymer backbone were subsequently hydrogenated with H2/Pd(C), leading to a SCLCP with a fully saturated hydrocarbon backbone. This polymer system had a very flexible polymer backbone but a stiff connection between the main chain and the mesogenic unit. The distance between two adjacent side chains was about 12 methylene units. This very flexible main chain allowed the polymer to organize into a LC mesophase. Both polymers - the unsaturated and the saturated -showed smectic liquid crystalline mesophases with almost the same transition temperatures (see Table 5). 

Table 6 Comparison of SCLCPs with different main chains based on the cyanobiphenyl-mesogen...

Based on previous work which showed that backbone rigidity correlates with mesophase behavior for SCLCPs bearing calamitic mesogens [64], the double bonds of the main chain in polybutadienes were hydrogenated, leading to pure saturated alkane main chains, poly-(XXIX-5)a and poly-(XXIX-10)a in Table 18. But in contrast to the studies of calamitic SCLCPs, no dependency of backbone rigidity on mesophase behavior could be estabhshed. 

X-ray characterization revealed non-conventional packing in the smectic phase. It represented a novel class of SCLCPs in which the main chain was not confined in-between the smectic layers but rather penetrated them. 

In contrast to ROMP, ADMET offers the possibility of synthesizing both side-chain and main-chain liquid crystalline polymers. The scope and limitations of ADMET are discussed in detail by Wagener et al. in this issue. We herein focus on a few contributions that used step growth polymerization methods to prepare MCLCPs and SCLCPs. 

Zhang and coworkers chose a base polymer alternative to poly(styrenesulfonate) and prepared SCLCP with a polysiloxane backbone [102]. Differently from the previous cases, side groups were linked to the main chain by covalent bonding. 

Many reviews [1-3] of SCLCPs describe the structure of the backbone (main chain), the spacer (flexible linkage), and the side group (mesogenic unit) of the SCLCP. For example, the most widely used backbones include polyacrylates or polymethacrylates, polysiloxanes, and polyphosphazenes po-ly-ct-chloroacrylates, itaconates, and ethylene oxides have also been reported. 

Polymeric liquid crystals can be classified into either of two types, thermotropic and lyotropic, according to their formation conditions, or three types, main-chain, side-chain and complex liquid crystalline polymer (MCLCP, SCLCP and CLCP,... 

It has been demonstrated that the photo-induced orientation of dye-containing SCLCPs can be used for reversible optical data storage [85 90]. FTIR polarization spectroscopy has been applied to monitor the orientation of the main chain and the mesogenic side-chains which are of critical importance in these storage processes [15, 91-94]. Here, some results obtained by laser irradiation of a homologous series... 

From the point of view of molecular architecture, as schematically shown in Figure 9.3, two types of LCP have been developed (1) main-chain LCPs (MCLCPs), having the monomeric liquid crystals (i.e., mesogenic group) in the main chain of flexible links, and (2) side-chain LCPs (SCLCPs), having the monomeric liquid crystals attached, as a pendent side chain, to the main chain. 

LCPs combine the mechanical properties of polymers with the order of LCs. The low molar mass mesogenic units, which form a LC phase, consist of a rigid core. If this core is extended, so-called main chain liquid crystalline polymers (MCLCPs) are obtained. A second method to obtain LCPs is to connect low molecular weight LC (LMWLC) units via flexible spacers. This approach allows the preparation of side chain liquid crystalline polymers (SCLCPs) (Box 1). 

There are different polymer structures that exhibit LC phases. The extension of the mesogen s rigid aromatic core leads to main chain polper systems. Other approaches are based on the spacer concept. Here rigid cores that are common in LMWLCs are decoupled by flexible alkyl chains. The mesogenic units can be placed either in the main or in the side chain. Also combined MCLCP/SCLCPs have been prepared (figure 3). 

Traditionally, two major classes of thermotropic liquid crystalline polymers have been identified the so called main chain (longitudinal) and side chain (comb) types (MCLCPs and SCLCPs, respectively) (Fig. 2.5). More recently other variants have appeared these are combined LCPs which are hybrid between MCLCPs and SCLCPs, and the rigid rod types described by Watanabe et A great wealth of literature already exists in the form of unified texts and reviews which detail both the major classes of LCPs. Bibliographic data have been compiled" and reviews more or less specific to main chain or comb " polymer systems have appeared. We shall be concerned here only with main chain and side chain LCPs. 

For example, the interplay between the backbone chain and the mesogenic side chains can make the nematic phase of scLCPs more complex than a normal nematic (cf. Section 4.3). The nature and magnitude of such an interlay may be expected to depend, to a large extent, on the length, stiffness and shape anisotropy of the otherwise weakly interacting spacer group linking the side chains to the main chain. In the... 

In the smectic phase of scLCPs, interactions between the liquid-crystalline and the backbone chain moieties takes a much more dramatic form. The side chains form the strongly interacting part of the smectic layers, while the weakly interacting backbone chain completes the layer and is basically excluded from the strongly interacting part. In a well-developed smectic phase the main chain thus finds itself very nearly confined to a two-dimensional plane within the smectic layers, with occasional interlayer hopping (see Fig. 4.13(c)). 

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