Chiral Side-chain Liquid Crystalline Research Articles

Effect of fluorinated nematic mesogens on phase behaviors and optical properties of chiral liquid crystalline polysiloxanes

A series of new chiral side-chain liquid crystalline polymers (P1–P7) have been synthesized with poly(methylhydrogeno)siloxane, two chiral liquid crystalline monomers, cholesteryl-4-allyloxybenzoate (M1) and cholesteryl 4-(10-undecylen-1-yloxy) benzoate (M2), and a nematic liquid crystalline monomer, 4-(trifluoromethyl)phenyl 4-(undec-10-enoyloxy)benzoate (M3). The chemical structures and liquid crystalline properties of the synthesized polymers have been investigated by FTIR, 1H-NMR, differential scanning calorimetry (DSC), polarizing optical microscopy (POM), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). All chiral polymers show wide mesophase temperature ranges and a high thermal stability with decomposition temperatures (T d) at 5 % weight loss greater than 300 °C. P1–P4 display a single cholesteric phase, but P5–P7 containing more fluorinated units show a smectic A (SA) phase besides a cholesteric phase. The optical properties of the polymers have been characterized by circular polarization spectra and optical rotation analysis. The cholesteric polymers P3 and P4 exhibit different colors at room temperature, and the color can remain over 24 months. The maximum reflection bands of polymers P1–P4 shift to long wavelength with increasing the content of M3 in the polymer systems. For P5–P7, the reflection wavelengths change sharply around the temperature of the SA–Ch phase transition. The specific rotation value of P2 smoothly decreases from −8.2° to −0.29° when it is heated, but the specific rotation value of polymer P7 changes from negative value to positive value on heating cycle. The optical properties of the polymers offer tremendous potential for various optical applications.

Synthesis and characterization of side-chain liquid crystalline polymers and oriented elastomers containing terminal perfluorocarbon chains

Several novel chiral side-chain liquid crystalline (LC) polysiloxane resins containing epoxy groups and mesogenic components have been graft copolymerized by a one-step hydrosilylation reaction with poly(methylhydrogeno)siloxane, an epoxy monomer 2-(allyloxymethyl)oxirane, and chiral fluorinated liquid-crystalline monomers 4′-(4-(allyloxy)benzoyloxy)biphenyl-4-yl 6-(perfluorooctanoyloxy)hexahydrofuro[3,2-b]furan-3-yl adipate and 4′-(4-(undec-10-enoyloxy)benzoyloxy)biphenyl-4-yl 6-(perfluorooctanoyloxy)hexahydrofuro[3,2-b]furan-3-yl adipate. The synthesized epoxy resins are cured using 4,4′-diaminodiphenyl-methane in mesophase state under a magnetic field to obtain crosslinked oriented elastomers. The chemical structures, LC properties and surface morphology of the monomers, the resins and the liquid crystalline elastomers (LCEs) are characterized by use of various experimental techniques such as FTIR, 1H NMR, EA, TGA, DSC, POM, and X-ray measurements. The mesomorphic properties of the synthesized resins and corresponding oriented elastomers are influenced by the terminal perfluorocarbon chains components effectively. The resins show chiral nematic and chiral smectic C phases (Sc*), and Sc* are frozen in their corresponding oriented elastomers. The LC phases are verified by X-ray measurements, and the orientational order parameters of the oriented LCEs are calculated as well.

Chiral Liquid Crystal Polymers Containing Electron Donor- Acceptor Action-Synthesis and Characterization

A series of new chiral side-chain liquid crystalline polymers with electron donor-acceptor action were prepared containing chiral monomer with donor group and nematic LC monomer with acceptor group. All polymers were synthesized by graft polymerization using polymethylhydro- siloxane as backbone. The mesomorphic properties were investigated by differential scanning calorimetry(DSC), polarizing optical microscopy(POM)，thermogravimetric analyses（TGA） and X-ray diffraction measurements(XRD). The chemical structures of monomers and polymers were confirmed by Fourier transform infrared (FTIR), proton nuclear magnetic resonance spectra(1H NMR and 13CNMR). M1 showed nematic phase and M2 turned out cholesteric phase on heating and cooling cycle. Polymers P3~P8 were cholesteric phase. Experimental results demonstrated that the glass transition temperatures and isotropization temperatures and the ranges of the mesophase temperature increased with increasing the content of chiral agent. All of the obtained polymers showed high thermal stability.

Synthesis and characterization of chiral liquid crystal polymers containing donor–acceptor group

A series of new chiral side-chain liquid crystalline polymers with electron donor–acceptor action were prepared containing chiral monomer with donor group and nematic LC monomer with acceptor group. All polymers were synthesized by graft polymerization using polymethylhydrosiloxane as backbone. The mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), thermogravimetric analyses (TGA), and X-ray diffraction measurements (XRD). The chemical structures of monomers and polymers were confirmed by Fourier transform infrared (FTIR), proton nuclear magnetic resonance spectra (1H NMR and 13CNMR). M1 did not show liquid crystalline phase and M2 turned out nematic phase on heating and cooling cycle. Polymers P2–P7 were cholesteric phase. Cholesteric phase and low glass temperature liquid crystalline polymers have been obtained, which offered the possibility of application. Experimental results demonstrated that the glass-transition temperatures rose and isotropization temperatures decreased and the ranges of the mesophase temperature reduced with increasing the content of chiral agent. All of the obtained polymers showed high thermal stability.

Effect of chiral isosorbide groups on mesomorphic properties of side-chain liquid-crystalline polysiloxanes

Chiral side-chain liquid-crystalline (LC) polysiloxanes containing isosorbide groups were graft copolymerised with poly(methylhydrogeno)siloxane, a chiral LC monomer 6-(4-methoxy-benzoyloxy)-hexahydro-furo[3,2-b]furan-3-yl 4'-(4-undec-10-enoyloxy-benzoyloxy)-biphenyl-4-yl adipate and a nematic LC monomer 4'-(4-methoxy-benzoyloxy)-biphenyl-4-yl 4-(2-undec-10-enoyloxy-ethoxy)-benzoate. The chemical structures and LC properties of the monomers and polymers were characterised by use of various experimental techniques including Fourier transform infrared spectroscopy (FTIR), 1H-nuclear magnetic resonance (NMR), element analyses (EA), differential scanning calorimetry (DSC), polarised optical microscopy (POM) and X-ray diffraction (XRD). All the chiral LC polymers showed LC properties with very wide mesophase temperature ranges and the chiral component in the LC polymer systems lead to the appearance of a cholesteric phase. The polymers bearing most chiral LC monomer component showed smectic phases by reason of regular structures in the polymer systems. With the increase of another nematic LC monomer in the polymers, the regular polymer structures were destroyed because of different chemical structures between the two kinds of LC monomers, leading to the disappearance of the smectic arrangement.

Chiral side-chain liquid crystalline polysiloxanes bearing fluorinated mesogens and cholesteryl groups

A series of chiral side-chain liquid crystalline (LC) polysiloxanes bearing fluorinated mesogens were synthesized with a cholesteric LC monomer and a fluorinated nematic LC monomer. They were characterized by use of various experimental techniques, and effect of fluorinated mesogens on characteristic of LC polysiloxanes was studied as well. In photoluminescence spectra, a narrow and a broad peak occur at around 270–317 nm, originated, respectively, from fluorinated phenyl groups and the conjugated xenene structure. The specific rotation analysis of all polymers showed negative values, but absolute values were lower than those of the chiral monomers. All polymers showed smectic LC phase with very wide temperature ranges on heating and cooling cycles. Especially, only polymers bearing more fluorinated component exhibited smectic–cholesteric phase transition when they were heated. As the polymers contained more fluorinated mesogens, segregation of the fluorinated segment to the surface should occur at mesomorphic temperature. The highly ordered lamellar mesogen–siloxane matrix systems should be disturbed severely by separation of fluorinated mesogens, suggesting mesogenic orders transition from lamellar smectic to cholesteric phase.

Small angle X-ray scattering study of chiral side chain liquid crystalline polymers in 5CB and 8CB solvents

Small angle X-ray scattering was used to examine the new chiral side chain liquid crystalline polyacrylates (P4M and P11M) and their mixtures (2 wt %) in the low molar mass nematogenics 4′-n-pentyl-4-cyanobiphenyl (5CB) and 4′-octyl-4-cyanobiphenyl (8CB). Complementary data were obtained by polarizing optical microscopy. In agreement with previous studies, the mesophases of the bulk polymers show a dependence on the aliphatic spacers linking the mesogenic units to the polymer backbone. Chiral nematic and smectic A1 phases were observed for the polyacrylates with four (P4M) and eleven (P11M) methylene units as spacers, respectively. In solution with 5CB and 8CB, P4M exhibits an injected smectic phase, whereas P11M maintains the smectic arrangement already observed in the bulk, with swollen smectic layers. In all the mixtures, layer stability was found to depend on the liquid crystal used as solvent, as well as on the temperature. At temperatures corresponding to the nematic 5CB and 8CB, the coexistence of two mesophases was observed in the mixtures. Moreover, with the liquid crystal solvents in the isotropic phase, microstructures suspended in the solvent matrix containing the liquid crystalline polymer in the smectic arrangement were detected.

Chiral liquid-crystalline block copolymers based on polyether and mesogenic polyacrylate blocks

Abstract New liquid-crystalline ABA triblock copolymers containing crystalline polytetrahydrofuran (A) and chiral side-chain liquid-crystalline (B) blocks were prepared, and their phase behavior was studied. Block B was one of different polyacrylates containing the biphenyl mesogen variously spaced from the backbone and substituted with chiral groups, that are known to exhibit an electroclinic response in the chiral smectic A phase of the relevant homopolymers. The copolymers appeared to be phase-separated and formed mesophases characterized by lower transition temperature and enthalpy than those of the corresponding polyacrylate homopolymers.

Synthesis and ring-opening polymerization of optically pure mesogenic malolactonates

Abstract Optically pure malolactonate monomers containing biphenyl mesogenic groups with either an ethylene or a hexamethylene spacer were prepared from optically pure malic acid and polymerized with alkylaluminoxane catalysts to form a series of new chiral side chain liquid-crystalline polymers, which contained the chiral centres in the backbone. The mesogenic malolactonate monomers were determined to be optically pure by 1H NMR spectroscopy of the β-lactone complexed with a chiral europium shift reagent. Both the methylaluminoxane and isobutylaluminoxane catalysts gave polymers having bimodal molecular weight distributions, the latter catalyst yielded a larger amount of the higher molecular weight fraction than the former. The polymers showed high optical rotations, high degrees of isotactic stereoregularity, and enantiotropic liquid-crystalline properties, all of which were influenced by the molecular weight distribution. Copolymers of malolactonate monomers with different spacers were also prepared an...

Chiral liquid crystal polymers with potential ferroelectric properties: Synthesis and characterization

Abstract The synthesis and thermal properties are described of new series of chiral side chain liquid crystalline polymers containing monomeric units constituted by a biphenylyl moiety variously spaced from the hydrocarbon backbone both in length and functionality. SA and chiral Sc phases were detected in different ranges of temperature whose onset and stability are dependent on the length and parity of the polymethylene spacer.