Structure et proprietes thermodynamiques de polyamides rigides portant ces groupes lateraux flexibles

Combined main chain/side chain polymers. A new class of liquid crystalline polymers with unusual structural, thermodynamic and dynamic properties

Abstract Combined main chain/side chain polymers carry rigid rod-like mesogenic units both in the side chain and along the chain backbone. The properties of such combined systems are expected to be controlled by the competition of the interactions between the mesogenic units in the side and main chains as well as the tendency of the chain backbones to maximize their entropy. The thermodynamic, structural and dynamic properties of such combined main chain/side chain liquid-crystalline polymers were investigated for various chain architectures. The combined systems were found to display properties corresponding in many cases to a favourable superposition of properties characteristic of both m…

Sanidics: A new class of mesophases, displayed by highly substituted rigid-rod polyesters and polyamides

Abstract The structure of rigid-chain polyesters and polyamides which possess flexible side chains consisting of methylene or 1,4,7-trioxaoctyl oxide units have been investigated by means of X-ray scattering. The X-ray studies were performed on fibres and monodomains. Additional information was gained from calorimetric, dilatometric and microscopic studies. The investigations revealed that these polymers display mesophases and that the structures of the mesophases differ from those observed for discotic and calamitic phases. They are characterized by the fact that in the ordered and disordered phases board-like molecules are stacked parallel on top of each other and that these stacks of mol…

Transient photoconductivity in a discotic hexagonal plastic crystal

Molecular dynamics of discotic charge-transfer complexes, dielectric spectroscopy and2H NMR studie

Abstract Using a combination of solid state 2H NMR spectroscopy on selectively deuteriated samples and dielectric spectroscopy, the molecular dynamics of discotic charge-transfer (CT) complexes were investigated. These complexes show particular thermodynamic and flow properties. Considered were mixtures of low molar mass donors and acceptors, low molar mass donors with main chain acceptor polymers and covalently linked donor-acceptor twins with different lengths of the spacer. A main result is that correlated rotational motions of discotic molecules or groups about the columnar axis are observed in all systems except for the twin with the short spacer. This type of motion seems to be a gene…

Fluoroalkylated discotic liquid crystals

Abstract The concept of mesophase stabilization by partial fluorination of side chains has been extended to discotic systems. The mesophase structure is essentially unchanged, whereas the temperature range of the mesophase is strongly affected by the fluorinated side chains. Triphenylene substituted with only one partially fluorinated side chain exhibits a decrease of the clearing temperature, whereas for symmetrically substituted systems a broad range mesophase has been observed. This behaviour can be attributed to a segregation of the incompatible parts of the molecule giving rise to a stabilized columnar structure for the symmetrical substitution pattern.

Polyreaktionen in orientierten Systemen, 3. Polymerisation ungesättigter Benzylidenaniline mit flüssig-kristallinen Eigenschaften

Die Acrylsaure- und Methacrylsaureester 3a–m wurden synthetisiert und auf ihr nematogenes Verhalten untersucht. Zwei Monomertypen wurden zur Untersuchung des Polymerisationsverhaltens herangezogen. Dabei zeigte sich, das die Polymerisationsgeschwindigkeit beim ubergang vom nematischen in den isotropen Bereich sprungartig ansteigt. In Abhangigkeit von der Darstellungsweise des Polymeren ergaben sich Unterschiede in der Struktur. Polymere, die bei 20°C in Losung dargestellt werden, sind amorph, wahrend Losungsmittel-polymerisate, die bei −78°C hergestellt und anschliesend getempert wurden, eine Struktur aufweisen, die mit der der Polymeren aus der nematischen Phase nahezu ubereinstimmt. Diese…

Polymer, Metal, and Hybrid Nano- and Mesotubes by Coating Degradable Polymer Template Fibers (TUFT Process)

). Selective reaction with the silver atoms at the interface of the particles occurred and the coated particles were then extracted from reverse micelles. The powder of coated nanocrystals thus obtained was then dispersed in hexane, giving an optically clear solution. The size distribution was still rather large (30 %), and to reduce it a size-selected precipitation process [20] was used. In this process two solvents, such as hexane and pyridine, are mixed. The first is a good solvent and the second a poor solvent for the alkyl chains. With this solvent mixture, the larger coated particles flocculated whereas the smaller ones remain in the solution, thus providing size selection. By repeati…

Reversible Digital And Holographic Optical Storafe In Polymeric Liquid Crystals (PLC)

A new reversible optical storage technique based on azo dye containing liquid crystalline polymers and copolymers is described. Monodomain films of the polymers were used as storage medium. Digital and holographic information was stored and reconstructed. The stored information can be erased and the writing process is repeatable. The storage process is explained in terms of a transcis isomerization of the mesogen inducing local director field distortions.

Small angle X-ray scattering from amorphous polymers arising from heterogeneities

The small angle X-ray scattering of glassy polymers (PET, PC, PVC, PMMA) and of polymer melts (PE) was studied. The dependence of the intensity scattered at small angles on the sample treatment suggests that neither the inherent structure of the pure polymer phase nor microholes are the origin of the scattering. In agreement with all experimental facts the scattering can be attributed to foreign particles such as for instance stabilizers in the polymer matrix. The consequence of this result is discussed with respect to the nodular structure of the amorphous phase and with respect to structural models of the amorphous phase. The nodular structure is not related to regions of different densit…

Structure and phase transitions of a liquid crystalline polymer

The structures, textures as well as thermodynamic properties of a side chain polymer exhibiting a liquid crystalline phase in addition to a partially crystalline state and the isotropic fluid state were investigated. Furthermore the kinetics of phase transitions between these states were analyzed. It was found that the properties of this polymer are intermediate between that of low molecular weight liquid crystals and common polymers. In particular it was observed that the relation between the liquid crystalline texture and the structure is different from that of low molecular weight liquid crystals and that the properties of the crystalline and liquid crystalline state depend strongly on t…

Polyreactions in oriented systems, VIII.. Polymerization of a liquid crystalline monomer under the influence of a high magnetic field

Nonlinear optical self diffraction effects for a light beam in a liquid crystalline polymer in its isotropic fluid state was observed. This effect is characterized by the absence of a threshold intensity, a diffraction pattern that does not depend on the polarization of the reading beam relative to that of the writing beam and which cannot be disturbed by transversally applied static electrical fields. This effect is attributed to a thermally induced spatial refractive index modulation. The time constants of the response are of the order of ms.

Structural variations of liquid crystalline polymers with phasmidic-type mesogens

Abstract The fixation of phasmidic-type mesogens through spacer groups to polysiloxane backbones provided a method of obtaining liquid crystalline polymers with phasmidic mesogens as side groups. The polymer 6b showed a bilayer structure in the mesophase range. The tendency to form liquid-crystalline phase depends on the number and the length of alkoxy substituents.

Micellar and lyotropic behavior of three isomeric bola-amphiphiles with pyridinium groups

The micellar and lyotropic phase behavior of three isomeric bola-amphiphiles 1, 2 and 3 based on para-, meta- and ortho-phenylene derivatives with hydrophilic pyridinium headgroups was investigated. The micellar behavior was characterized by surface-tension and conductivity measurements: while the para-substituted amphiphile 1 and the ortho isomer 3 aggregated to micelles, the meta-substituted amphiphile 2 exhibited stepwise, but discontinous self-association. This is explained by the mass-action and phase-separation model. The existence of “premicellar” aggregates and the discontinous aggregation of 2 is evidenced in addition by a difference-spectro-photometric measurement. The low surface…

Structure formation in doped discotic polymers and low molar mass model systems

Abstract Doping of low molar mass materials or polymers, possessing disc-like units, with electron acceptors leads to the stabilization of columnar discotic phases or even to the induction of such phases in compounds which either display a nematic discotic phase or only an amorphous phase in the absence of the electron acceptor. The induced columnar phase corresponds frequently to a hexagonally ordered one. We have observed, however, in addition the induction of new columnar phases such as the rectangularly ordered (Dro) and the columnar nematic phase (Nc). The enhancement of the tendency towards the formation of columnar phases is a consequence of electron acceptor—electron donor complex f…

The dielectric relaxation properties of a combined main-chain/side-chain liquid-crystalline polymer were investigated. It was found that the rotation of the side chain about the main chain (δ-process) is not as strongly restricted as in side-chain liquid-crystalline polymers. This is attributed to the facts that the side chain is attached to the flexible spacer within the chain backbone and that the concentration of the side chains is comparatively small. Two low-temperature relaxation processes were observed to occur in the glassy smectic and the crystalline state. They are attributed to intramolecular motions with in the mesogenic groups.

Komplexierung von Übergangsmetall-Ionen mit substituierten Azamakrocyclen: Induktion columnarer Mesophasen durch molekulare Erkennung

The synthesis and the thermotropic phase behavior of the dipolar amphiphiles C 5 H 5 N + (CH 2 ) m OCOPhPHCOO(CH 2 ) m N + C 5 H 5 and the polymeric amphiphile [(CH 2 ) 6 OPhPhO(CH 2 ) 6 OCOCH([CH 2 ] 6 N + C 5 H 5 )COO] n are described

Modes of Structure Formation in Doped Discotic Polymers and Low Molar Mass Model Systems

By doping low molar mass or polymeric liquid crystals containing flat disc-like units with electron acceptors one achieves a stabilization of columnar phases, the induction of a columnar phases in otherwise discotic nematic or even in amorphous systems. Theoretical models based on the assumption of strong electron donator-acceptor (EDA) complex formation are able to account for the structure formation on a molecular level and the thermodynamic properties of the mixtures and the model of diffusion limited aggregation (DLA) for the structure formation on a supermolecular structure.

Thermal density fluctuations in amorphous polymers as revealed by small angle X-ray diffraction

In the case of equilibrium the mean square relative fluctuations of the thermodynamic parameters vanish asymptotically as the number of degrees of freedom approach infinity. There are various observable effects, however, which are related to local fluctuations of the thermodynamic quantities within small parts of the macroscopic system. In particular the scattering of electromagnetic waves by a one-component, one-phase system is due to thermal density fluctuations within small volumes V of the sample. Considering a grand canonical ensemble the phenomenological theory of local fluctuations (1) for a one component system shows that the fluctuation of the number of particles N in the volume V …

Liquid crystal polymers from swallow-tailed mesogens

Abstract Swallow-tailed compounds containing an acetylenic unit have been synthesized. Only those compounds with a three ring structure exhibited liquid-crystalline phases. The platinum catalysed addition of these monomers to compounds containing Si-H groups was used to synthesize polymeric materials. Only those polymers with the tetramethyldisiloxane unit showed mesophases. The synthesis, characterization, and phase behaviour are described.

Chain conformation and structure in amorphous polymers as revealed by X-ray, neutron, light and electron diffraction

Abstract The physical structure of the melt, the supercooled melt, and the glassy state of amorphous polymers can be characterized by the chain conformation, the local order, and the morphology. The conformation was studied by small-angle neutron scattering. The local order was characterized by pair distribution functions which were derived from electron scattering curves. In addition, model calculations were used to gain information about short-range order. The morphology was studied by means of light scattering (density and anisotropy fluctuations), small-angle X-ray scattering (density fluctuations), and magnetic birefringence measurements (orientational order). Experiments were performe…

The synthesis and the results of the structural study of two copolysiloxanes with laterally fixed trinitrofluorenone (TNF) units is reported. The two copolysiloxanes having 2,4 (1a) and 5,3 (1b) dimethylsiloxane comonomer units per TNF side group differ significantly in their phase behaviour as evident from optical microscopy, differential scanning calorimetry and X-ray scattering: 1b shows a nematic mesophase whereas 1a is an amorphous material. The different phase behaviour is discussed in terms of microphase separation between the siloxane backbone and TNF side groups.

The synthesis of a new type of combined polymers containing both disc- and rod-like mesogens is reported. The polyesters, having a triphenylene derivative as a discotic mesogen in the side group and azobenzene or biphenyl derivatives as rod-like mesogens in the main chain were characterized by polarizing microscopy, differential scanning calorimetry, and X-ray scattering studies. The homopolymer 7 is highly crystalline, while the copolymer 8 is amorphous, both, however, do not form liquid-crystalline phases.

Structure and morphology of liquid-crystalline polymers

Liquid-crystalline phases are characterized by structures intermediate between a three-dimensionally ordered crystal and a disordered fluid. Polymers with liquid-crystalline structures can be obtained from specific monomers containing mesogenic groups with a tendency to form liquid-crystalline phases. These mesogenic groups are either incorporated into the main chain or attached to a chain as side groups. In both cases liquid-crystalline structures, and also enantiotropic liquid-crystalline phases, have been reported. Smectic polymers are characterized by layered structures with long-range order in the direction of the layer normal and two-dimensional short-range order within the layers. Th…

It is shown that the acceptor polyesters [(CH 2 ) x OCOC(=R) COO(CH 2 ) x ] n (R=9-[2,4,7-trinitrofluorenylidene]) x=3, 6, 8) influence the chain behaviour of the discotic hexapentyloxytriphenylene without changing the phase type (D ho ). The clearing temperature of the complexes has a maximum value when x=G. Both intra- and intercolumnar distance are smaller than in the pure discotic compound and independant of the spacer