The relaxation of electric field-induced polar orientation in a side-chain-bearing liquid-crystalline polysiloxane was measured
by means of thermally stimulated depolarization currents. Different relaxation mechanisms were identified and characterized:
the glass transition cooperative relaxation exhibits compensation behaviour. On the other hand, lowerTg and upperTg discharges were observed and their molecular nature is discussed.
This paper is concerned with an analysis of the thermodynamics and kinetics of mesophase formation by cooling from the isotropic state of side-chain liquid crystalline polycarbosilanes containing spacers in the range from 3 to 11 CH2-groups. The polymers are characterized by their thermotropic behaviour as far as temperature, enthalpy and entropy of the transitions are concerned. The kinetics was followed by optical and calorimetric methods. Longer spacer length leads to more perfect ordering in the mesophase, higher isotropization temperatures, and lower glass transition temperatures. The Avrami and Ozawa formalism to describe the transition kinetics to the mesophase from the isotropic state cannot be interpreted as the nucleation and growth mechanism known from crystallization.
Authors:S. Radhakrishnan, N. Somanathan, T. Narashimhaswamy, M. Thelakkat, and H. Schmidt
of thiophenes containing mesogenic side chains at the 3rd
position are synthesized. The thermal transitions and thermal stability of
the synthesized monomers and polymers are studied. The polarizing microscopic
studies of synthesized monomers showed nematic liquid crystalline phase and
these mesophases further confirmed by differential scanning calorimetric study.
The obtained melting and the isotropic temperatures decrease linearly with
the increase of aliphatic chain length. The transition temperatures determined
from DSC analysis, overlap well with the temperatures obtained from optical
microscopy studies. Thermal stability of the compounds is analysed using thermogravimetric
studies. Thermal stability of monomers and polymers has been determined by
calculating IPDT values. Structural influence on thermal degradation patterns
of monomers and polymers are also discussed.
Thermal properties of acrylate and methacrylate monomers containing long-fluorocarbon chains (H(CF2)nCH2OCOCH=CH2, (FnA) and H(CF2)nCH2OCOC(CH3)=CH2, (FnMA), wheren=6, 8, 10) and their comb-like polymers have been investigated by differential scanning calorimeter (DSC) and X-ray diffraction.
The comb-like polymers (PF10A and PF10MA) with sufficiently long-fluorocarbon chains showed a simple melting and crystallizing behavior. For the fusion of PF10A in 1st heating, enthalpy change δHf was 18 kJ mol−1 and entropy change δSf was 45 J K−1 mol−1, while for PF10MA the values δHf and δSf were 5.3 kJ mol−1 and 14 J K−1 mol−1, respectively. Melted PF8A crystallized slowly, whereas PF8MA with same fluorocarbon chain and also both of PF6A and PF6MA with shorter fluorocarbon chains can hardly crystallize by the aggregation of side-chains. Effects of the length of side-chain
and the flexibility of main chain on the side-chain crystallization of comb-like polymers are clear. Crystallization process
of the methacrylate monomers was sensitively affected by the scanning rate of DSC measurement and the length of fluorocarbon
It is shown that insertion in methacrylic polymers of bulky electron donor/acceptor side-groups with taper-shaped flourinated tails promotes a self-organization of the respective side-chain polymers due to the space demands of the bulky D/A side-groups, leading to a columnar hexagonal mesophase. The presence of an Lc-phase is evidenced by DSC and identified by X-ray analysis. The orientation in the respective copolymers and polymer blends is additionally improved by the CT-interaction between the D/A side-groups. An increased packing effect due to this CT-orientation effect is evidenced in DSC by an increase of the respective transition temperatures. CT-interaction is responsible as well for a preferential polymerization of monomeric D/A-complexes leading to copolymers of alternating structures and for a zip-like arrangement along the main chain of the A/D-complexes between the interacting side-groups in polymer blends. Formation of mesophases is even observed in CT-interacting blends between the Lc-D/A side-chain polymethacrylates and the respective amorphous D/A side-chain polysiloxanes.
To understand better the antagonistic behaviour of the backbone in comparison with the mesogenisity of the pendant side groups
in side-chain liquid crystal polymers series of measurements using mechanical spectroscopy as well as DSC were carried out
on two disubstituted polynorbornene derivatives.
In order to clarify the specific arrangement of chains, the influence of thermal history on the smectic phase stabilisation
were studied. By quenching samples from different temperatures, it was possible to obtain the systems which were either in
the glassy liquid-crystalline (LC) state or in the glassy isotropic amorphous state. The samples prepared in such ways were
used to study the influence of the LC structure on the mobility of chains in amorphous regions. The quality model of the supermolecular
structure of the LC polymers is proposed.
Authors:N. Buzás, L. Nagy, H. Jankovics, R. Krämer, E. Kuzmann, A. Vértes, and K. Burger
Triphenyltin(IV) complexes ofN-acetylglycine,N-acetyl-L-leucine,N-acetyl-L-asparagine andN-acetyl-L-tyrosine were prepared by two methods and characterized by means of different spectroscopic methods (FTIR, multinuclear,1H,13C and119Sn NMR and119Sn Mössbauer). The spectroscopic data indicated that theN-acetylglycine complex adopts a trigonal-bipyramidal structure in which the monodentate carboxylate and the amide-C=O group
are bound to the same organotin(IV) moiety. The other three complexes are linear oligomers in which the planar Ph3Sn(IV) is coordinated axially by a monodentate carboxylate and an amide-C=O from two different ligands. At theC-terminal end of the oligomer chain there is a tetracoordinated tin(IV) with a monodentate carboxylate as donor group.
Vinylated polyhedral oligomeric silsesquioxane (POSS-M) was prepared by the reaction of POSS containing amine groups with
acrylic acid. Azobenzene liquid crystalline copolymer (LCP-POSS) was then synthesized with 6.0 mol% POSS-M and 94.0 mol% acrylate
monomer containing azobenzene liquid crystalline moiety (Azo-M) by free-radical copolymerization. Homopolymer of Azo-M (LCP)
was also synthesized under the same conditions. Their thermal properties and liquid crystallinity were characterized by Thermal
gravimetric analysis (TG), differential scanning calorimetry (DSC), Wide-angle X-ray diffraction experiments (XRD) and polarized
optical micrographs (POM). The results showed that LCP-POSS has higher thermal stability and glass transition temperature
than pure LCP due to the incorporation of the rigid cage-like POSS. Especially, LCP-POSS exhibits enantiotropic smectic and
nematic liquid crystalline behaviors, its smectic-nematic transition temperature (TSN) and nematic-isotropic transition temperature (TNI) are higher than those of pure LCP, which may promote and extend its applications on stimuli-responsive materials and devices.
Authors:T. Yamada, S. Boyer, T. Iyoda, H. Yoshida, and J. Grolier
The effects of nitrogen (N2) pressure on amphiphilic di-block copolymer, PEO114-b-PMA(Az)40, were investigated by scanning transitiometry. The isotropic transition temperature increased with the increase of pressure
above 20 MPa. The hydrostatic pressure effects evaluated with the Clapeyron equation were smaller than the value obtained
by mercury as a pressurizing medium because the amount of absorbed gas decreases the volume change at the isotropic transition.
Authors:H. Hatakeyama, T. Yoshida, and T. Hatakeyama
Cellulose acetate-based polycaprolactones (CAPCL's) were synthesized by the polymerization of -caprolactone which was initiated by non-substituted OH group in cellulose acetate. The CL/OH (mol mol–1) ratios of the CAPCL's were changed from 2 to 20. Thermal and viscoelastic properties of the CAPCL sheets were studied by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Glass transition, cold crystallization and melting were determined by DSC. Dynamic modules (E'), dynamic loss modules (E'') and tan were measured in a temperature range from –150 to 50°C by DMA. Apparent activation energy of a dispersion was calculated from the frequency dependency of E'' peak temperature. It was found that the main chain motion of both CA and PCL is observed in a CL/OH ratio from 0 to 10 mol mol–1. However, when CL/OH ratio exceeds 10 mol mol–1, the crystalline region which is rearranged by the PCL chain association is observed and only the main chain motion of PCL can be detected.