Main-chain thermotropic liquid-crystalline polymers

Thermotropic main chain liquid crystalline polymers, MCLCPs... 

H.K.F. Cheng, T. Basu, N.G. Sahoo, L. Li, S.H. Chan, Current advances in the carbon nanotube/thermotropic main-chain liquid crystalline polymer nanocomposites and their blends. Polymers 4 (2) (2012) 889-912. 

Heino, M. (1994) Blends of thermotropic main-chain liquid crystalline polymers and thermoplastics. Acta Polytechnica Scandinavica, Chemical Technology and Metallurgy Series, No. 220, 1-49 (+ 7 appended publications). 

Thermotropic, main-chain, liquid-crystalline polymers (LCPs) have attracted considerable attention as a result of their high stiffness and mechanical properties. There has been interest in combining the LCPs with other materials. In one area, LCPs are used, in relatively low concentration, to reinforce less-stiff materials. In another case, a second component is used as a solvent to increase the mobility in the LCP and form lyotropic liquid-crystalline materials. There are now two reports, from Kricheldorf s group, of blends of PCL with liquid-crystalline polyesters [156,157]. 

The thermotropic aromatic main chain liquid crystalline polymers are also prepared by the phase transfer catalyzed aromatic nucleophilic polymerization [87]. Polyetherification of bis(4-chloro-3-nitrophenyl) sulfone with mesogenic aromatic diols is shown below ... 

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. 

This paper presents some of our results on the synthesis and structure of thermotropic main-chain liquid crystalline polyethers based on bis(4-hydroxy-phenoxy)-p-xylene. It also deals with two areas in the field of liquid crystalline polymers that have received only little attention, namely the dielectric relaxation (5-10 and Gedde, U.W. Liu, F. Hult, A. Gustafsson, A. Jonsson, H. Boyd, R.H. Polymer submitted) and the kinetics of isotropic-mesomorphic state transitions (11-14. 32). They are both very important for the understanding of the nature of the mesomorphic state in polymers and for the understanding of similarities and differences of physical phenomena between liquid crystalline and semi-crystalline polymers. 

Although studies concerning main chain liquid crystalline polymers were originated by Onsager (la) and Ishihara (lb) in the late 1940 s, extensive work in this field did not really begin until the early 1970 s. Jackson and Kuhfuss (2) reported the first thermotropic polyester by modifying polyethylene terephthalate with various amounts of p-hydroxybenzoic acid (HBA). They found that the copolyester with HBA content of at least 35 mole % have opaque melts. Subsequent studies in the area of aromatic polyesters by various authors resulted in a large number of patents and publication. (3.) These polymers were all derived from unsubstituted and... 

To date, reports of investigations on the gas transport properties of main chain liquid crystalline polymers appear to have been limited to the work conducted in our laboratory. Chiou and Paul (4.) have briefly described the transport parameters of an extruded film of an LCP having a similar structure to the commercial product Vectra. This copolyester belongs to the family of napthylene thermotropic polymers (NTP s) commercialized by Hoechst-Celanese Corp. whose synthesis and properties have been described previously (iLS.). Transient permeation experiments were conducted with a series of gases. The effective... 

Banded textures are observed in different oriented main-chain liquid crystalline polymers, e.g. in Kevlar fibres and in other lyotropics and thermotropics. The reason for the banding is that molecules after shearing are oriented according to a serpentine. The average direction of the serpentine is parallel to the shear direction. The exact mechanism for the generation of the serpentine structure is not known. 

Rigid-rod polymers are often liquid crystalline polymers classified as lyotropic, such as the aramid Kevlar (DuPont), or thermotropic liquid crystalline polymers, such as Vectran (Celanese) (see Polyamides, Aromatic Liquid Crystalline Polymers, Main-Chain Liquid Crystalline Thermosets). 

Donnio B, Wermter H, Finkelmann H (2000) A simple and versatile synthetic route for the preparation of main-chain liquid-crystalline elastomers. Macromolecules 33 7724—7729 Finkelmann H (1987) Liquid crystal polymers. Chap 1. In Gray GW (ed) Thermotropic liquid crystals. Wiley, Chichester, pp 1-27... 

This chapter is concerned with the synthesis of main chain, liquid crystal polymers, but only with the reactions used to prepare polyesters and polyamides. At the time of this review, polyesters have been of interest only as thermotropic polymers and polyamides for lyotropic behaviour, but this situation will, likely, soon change. There are undoubtedly aromatic polyesters which show liquid crystallinity in solution, and a thermotropic polyurethane has recently been reported. ... 

Low-molecular-weight liquid-crystalline compounds have been known for about 100 years. However, main chain liquid crystal polymers (MCLCPs) have attained prominence only in the last 15 years. In 1956 Flory predicted lyotropic behaviour and this theoretical prediction was well demonstrated in the synthetic polymer area with the discovery by Kwolek of the aramids, e.g. poly(/ -phenyleneterephthamide). This led to interest in thermotropic main chain LCPs and, although aromatic polyesters which are thermotropic were described during this period in patents issued to and Carborundum Co., their liquid-crystalline... 

Some particularities of the extraction of ions from an aqueous organic phase, and of the phase catalyzed polyetherification will be summarized. These will represent the fundamentals of our work on the synthesis of some novel classes of functional polymers and sequential copolymers. Examples will be provided for the synthesis of functional polymers containing only cyclic imino ethers or both cyclic imino ethers as well as their own cationic initiator attached to the same polymer backbone ABA triblock copolymers and (AB)n alternating block copolymers and a novel class of main chain thermotropic liquid crystalline polymers containing functional chain ends, i.e., polyethers. 

Three major topics of research which are based on phase transfer catalyzed reactions will be presented with examples. These refer to the synthesis of functional polymers containing functional groups (i.e., cyclic imino ethers) sensitive both to electrophilic and nucleophilic reagents a novel method for the preparation of regular, segmented, ABA triblock and (A-B)n alternating block copolymers, and the development of a novel class of main chain thermotropic liquid-crystalline polymers, i.e., polyethers. 

Figure 1.69 General structure of main-chain (M.C.) and side-chain (S.C.) LCPs. Adapted from T. S. Chung, The recent developments of thermotropic liquid crystalline polymers. Polymer Engineering and Science, 26(13), p. 903. Copyright 1986, Society of Plastics Engineers.

Thermotropic liquid crystalline polymers, like polyesters containing mesogenic units on the main chain, may not be described by the wormlike chain model (cf. Sect. 1.2). The present article does not consider this type of polymers. 

Jo, B. W. and Lenz, R. W. Liquid crystalline polymers, 7, thermotropic polyesters with main chain phenyl- 1,4-phenylene, 4,4 -biphenylene, and 1,1 -binaphthyl-4,4 -ylene units. Makromol. Chem. Rapid Commun. 3, 23 (1982)... 

The development is reviewed of liquid-crystalline polymers whose mesophase formation derives from the nature of the chemical units in the main chain. The emphasis lies primarily on highly aromatic condensation polymers and their applications. The general properties of nematic phases formed by such polymers are surveyed and some chemical structures capable of producing nematic phases are classified in relation to their ability to form lyotropic and thermotropic systems. The synthesis, properties, physical structure and applications of two of the most important lyotropic systems and of a range of potentially important thermotropic polymers are discussed with particular reference to the production and use of fibres, films and anisotropic mouldings. 

Academic and industrial interest in liquid-crystalline polymers of the main-chain type has been stimulated by certain special properties shared by lyotropic and thermotropic systems that exhibit a nematic phase. Although these special properties affect both the processing into fibres and other shaped articles and the physical behaviour of the products, the product behaviour is at least partly attributable to the novel processing behaviour. 

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