Synthesis and characterization of liquid crystalline elastomers bearing fluorinated mesogenic units and crosslinking mesogens

Several new side‐chain liquid crystalline (LC) polysiloxanes and elastomers ( IP ‐ VIP ) bearing fluorinated mesogenic units and crosslinking mesogens were synthesized by a one‐step hydrosilylation reaction with poly(methylhydrogeno)siloxane, a fluorine‐containing LC monomer 4′‐undec‐10‐enoyloxy‐biphenyl‐4‐yl 4‐fluoro‐benzoate and a crosslinking LC monomer 4′‐(4‐allyloxy‐benzoxy)‐biphenyl‐4‐yl 4‐allyloxy‐benzoate. The chemical structures and LC properties of the monomers and polymers were characterized by use of various experimental techniques such as FTIR, ¹H‐NMR, EA, TGA, DSC, POM and XRD. The effect of crosslinking mesogens on mesomorphic properties of the fluorinated LC polymers was studied as well. The obtained polymers and elastomers were soluble in many solvents such as toluene, tetrahydrofuran, chloroform, and so forth. The temperatures at which 5% weight loss occurred (T_d) were greater than 250°C for all the polymers, and the weight of residue near 600°C increased slightly with increase of the crosslinking mesogens in the fluorinated polymer systems. The samples IP , IIP , IIIP and IVP showed both smectic A and nematic phases when they were heated and cooled, but VP and VIP exhibited only a nematic mesophase. The glass transition temperature (T_g) of polymers increased slightly with increase of crosslinking mesogens in the polymer systems, but the mesophase–isotropic phase transition temperature (T_i) and smectic A–nematic mesophase transition temperature (T_S‐N) decreased slightly. It suggests that the temperature range of the mesophase became narrow with the increase of crosslinking mesogens for all the fluorinated polymers and elastomers. In XRD curves, the intensity of sharp reflections at low angle decreased with increase of crosslinking mesogens in the fluorinated polymers systems, indicating that the smectic order derived from fluorinated mesogenic units should be destroyed by introduction of more crosslinking mesogens. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and characterization of fluorinated liquid-crystalline elastomers containing chiral liquid-crystalline crosslinking units

Fluorinated chiral liquid-crystalline elastomers (LCEs) were graft copolymerized by a one-step hydrosilylation reaction with polymethylhydrogenosiloxane, a fluorinated LC monomer 4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyloxy)phenyl 4-(undec-10-enoyloxy)benzoate (PPUB) and a chiral crosslinking LC monomer (3R,3aR,6S,6aR)-6-(undec-10-enoyloxy)hexahydrofuro[3,2-b]furan-3-yl 4′-(4-(allyloxy)benzoyloxy)biphenyl-4-carboxylate (UHAB). The chemical structure, liquid-crystalline behavior and polarization property were characterized by use of various experimental techniques. The effective crosslink density of the LCEs was characterized by swelling experiments. The thermal analysis results showed that the temperatures at which 5% weight loss occurred were greater than 250 °C for all the LCEs, and the residue weight nearby 600 °C increase with increasing chiral crosslinking components in the polymer systems. All the samples showed chiral smectic C mesophase when they were heated. The glass transition temperature and mesophase-isotropic phase transition temperature of fluorinated elastomers increased slightly with increase of chiral crosslinking mesogens in the polymer systems, but the enthalpy changes of mesophase-isotropic phase transition decreased slightly. In XRD curves, all the samples exhibited strong sharp reflections at small angles suggesting smectic layered packing arrangement. These fluorinated chiral LCEs showed 0.1–0.2 μC/cm² of spontaneous polarization with increasing chiral crosslinking component.     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4′‐allyloxybiphenyl 4′‐ethoxybenzoate, M₁ ), a chiral crosslinking agent (isosorbide 4‐allyloxybenzoyl bisate, M₂ ) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂ . The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X‐ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂ –P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145–209.6°C, with no changed on the cooling. Polymers P₄ –P₇ , with more than 6?mol?% of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15?mol?% of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

Side-chain cholesteric liquid-crystalline elastomers containing azobenzene derivative as cross-linking agent – synthesis and characterisation

The cholesteric polysiloxanes (PLQ series) were obtained by reacting cholesteric monomer and phenolic hydroxyl monomer in different ratios with polysiloxanes. The chiral azo-containing polysiloxanes liquid-crystalline elastomers (LCEs) were synthesised by esterifying PLQ series with acyl acid of azo diacid catalysed by 4-dimethylaminopyridine (DMAP). The chemical structures and mesomorphic properties of monomers and polymers were confirmed by conventional spectroscopic methods. The elastomers displayed elastic properties, reversible phase transition and high thermal stability. The T_g values changed irregularly and T_i values decreased at the beginning and then increased afterwards. The chiral azo-LCEs showed colourful textures and a Grandjean texture could be observed, which exhibited a red shift with increasing content of azo moiety. PLQ₂–PLQ₆ exhibited selective reflection in the visible light region, but PLZ₁–PLZ₄ can only observe selective reflection when appropriate mechanical pressure was imposed on the polymers. The PLZ series was carefully investigated by ultra violet–visible spectroscopy.     

Side-chain cholesteric liquid crystalline elastomers containing isosorbide as chiral agent – synthesis and characterisation

In this work the new-style nematic monomer M₁ , chiral crosslinking reagent M_C and a series of new side-chain cholesteric liquid crystalline elastomers derived from M₁ and M_C were prepared. The effect of the content of the chiral crosslinking unit on phase behaviour of the elastomers has been discussed. Polymer P₁ showed nematic phase, P₂ –P₇ showed cholesteric phase, P₃ formed Grandjean texture in the heating cycle and turned out a blue Grandjean texture in the cooling cycle, P₂ –P₃ with less than 6 mol% of chiral crosslinking agent gave rise to selective reflection. The elastomers containing less than 15 mol% of the crosslinking units displayed elasticity, reversible phase transition and high thermal stability. Experimental results demonstrated that the glass transition temperatures reduced first and then increased, and the isotropisation temperatures and the mesophase temperature ranges decreased with increasing content of crosslinking unit.     

Synthesis and characterisation of chiral liquid crystalline elastomers containing four-arm crosslinking agent

A new series of side-chain chiral liquid crystalline elastomers derived from M₁ (cholest-5-3-ol(3β)-4-(2-propen-yloxy)]benzoate) and M_C(2,5-[3,5-bis(4-(3-(4-(allyloxy)phenyl)propanoyloxy)benzoyloxy)benzoic acid]isosorbide diester). The structures of monomers and elastomers measured by using Proton Nuclear Magnetic Resonance Spectra (¹H-NMR) and Fourier transform infrared spectroscopy (FTIR) separately are consistent with our design. IIP~VIP all appeared blue Grandjean (GJ) texture on the heating cycle or cooling cycle. The glass sheets of IIP~VIP were made under 150°C and measured its ultraviolet–visible spectrophotometry by PerkinElmer Lambda 950 instrument (Shelton, CT, USA). IIP~VIP all have absorptions at about 481~483 and 561~562 nm. The optical activities were measured at different temperatures on heating and cooling cycles. And the blue selective reflection of IIP~VIP on the round glass sheet can be seen. The elastomers containing less than 6 mol% of the crosslinking units displayed elasticity, reversible phase transition and high thermal stability. The glass transition temperatures reduced first and then increased, the isotropisation temperatures and the mesophase temperature ranges increased first and then decreased with increasing content of crosslinking unit. The thermogravimetric analysis (TGA) results showed that the temperatures at which 5% weight loss occurred (T_d) were greater than 310°C for all the polymers.     

Synthesis and characterization of side-chain cholesteric elastomers derived from an isosorbide crosslinking agent

New liquid crystalline monomer 4-(4-ethoxybenzoyloxy)biphenyl-4′-[(10-undecylen-1-yloxy)-4′-ethoxy]benzoate (M ₁ ), chiral crosslinking agent isosorbide di-(10-undecylen-1-yloxybenzoate) (M ₂ ), and the corresponding elastomers were prepared. The chemical structures of M ₁ and M ₂ were characterized by Fourier transform infrared and ¹H-nuclear magnetic resonance. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction measurements. M ₁ exhibited typical threaded texture and droplet texture of nematic phase. The use of chiral crosslinking agent in the polymer networks could induce cholesteric phase. The elastomers containing less than 10 mol% of the chiral crosslinking units showed elasticity, reversible phase transition, wide mesophase temperature ranges, and high thermal stability. For the elastomers P ₂ –P ₄ , the glass transition temperature (T _g) increased; clearing temperature (T _i) and mesophase temperature range (ΔT) decreased with increasing content of the crosslinking unit.     

Synthesis and characterization of a series of side chain chiral smectic liquid crystalline elastomers

A series of new chiral smectic liquid crystalline elastomers was prepared by graft polymerization of a nematic monomer with a chiral and non‐mesogenic crosslinking agent, using polymethylhydrosiloxane as backbone. The chemical structures of the monomers and polymers obtained were confirmed by FTIR and ¹H NMR. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X‐ray diffraction. Monomer M ₁ showed a nematic phase during heating and cooling. Polymer P ₀ exhibited a smectic B phase; elastomers P ₁–P ₃ showed the smectic A phase, P ₄–P ₆ showed a chiral smectic C(SmC*), and P ₇ displayed stress‐induced birefringence. Elastomers containing less than 15?mol?% M ₂ displayed elasticity, reversible phase transitions with wide mesophase temperature ranges, and high thermal stability. With increasing content of the crosslinking unit, glass transition temperatures first increased, then fell, then increased again; isotropization temperatures and mesophase temperature ranges steadily decreased.     

Thermal characterisation of thermotropic nematic liquid-crystalline elastomers

Nematic liquid-crystalline elastomers (LCEs) are weakly cross-linked polymeric networks that exhibit rubber elasticity and liquid-crystalline orientational order due to the presence of mesogenic groups. Three end-on side-chain nematic LCEs were investigated using real-time synchrotron wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), and thermogravimetry (TG) to correlate the thermal behaviour with structural and chemical differences among them. The elastomers differed in cross-linking density and mesogen composition. Thermally reversible glass transition temperature, T_g, and nematic-to-isotropic transition temperature, T_ni, were observed upon heating and cooling. By varying the heating rate, T_g⁰ and T_ni⁰ were determined at zero heating rate. The temperature dependence of the orientational order parameter was determined from the anisotropic azimuthal angular distribution of equatorial reflections seen during real-time WAXS. Results show that the choice of cross-linking unit, its shape, density, and structure of co-monomers, all influence the temperature range over which the thermal transitions take place. Including multi-ring aromatic groups as cross-linkers increased the effective stiffness of the cross-linking, resulting in a higher glass transition temperature. The nematic-to-isotropic transition temperature increased in the presence of multi-ring aromatic structures, as either cross-linkers or mesogens, particularly when the multi-ring structures were larger than the low-molar-mass mesogen common to all three samples.     

Effect of terminal perfluorocarbon chain containing mesogens on phase behaviors of chiral comb-like liquid crystalline polymers

A novel perfluorinated liquid crystal 4′-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyloxy)biphenyl-4-yl undec-10-enoate (PFOBU) was synthesized, which exhibited smectic C phase. Several liquid crystalline polymers (PI–PVI) were synthesized by use of poly(methylhydrogeno)siloxane, PFOBU, and cholesteryl 3-(4-allyloxy-phenyl)-acryloate. The chemical structures and liquid crystalline (LC) properties of the monomers and polymers, and some ferroelectric properties of the chiral smectic C (S_C^*) phase were characterized by use of various experimental techniques. The effect of perfluorocarbon chains on phase behaviors of the fluorinated LC polysiloxanes was studied as well. PI and PII showed single chiral nematic (N^*) mesophase when they were heated and cooled, but PIII, PIV, PV, and PVI containing more perfluorocarbon chain units exhibited S_C^* phase besides N^* mesophase. Introduction of perfluorocarbon chain containing mesogens to the chiral cholesteryl-containing polymer systems resulted in a S_C^* mesophases, indicating that the fluorophobic effect could lead to microphase segregation and modifications of smectic mesophases from the chiral nematic phase.     

Preparation and phase behavior of side‐chain cholesteric liquid‐crystalline elastomers

A series of new side‐chain cholesteric elastomers derived from cholesteryl 4‐(10‐undecylen‐1‐yloxy)‐4′‐ethoxybenzoate and phenyl 4,4′‐bis(10‐undecylen‐1‐yloxybenzoyloxy‐p‐ethoxybenzoate) was synthesized. The chemical structures of the monomers were confirmed by elemental analyses, Fourier transform infrared, and ¹H NMR and ¹³C NMR spectra. The mesomorphic properties of elastomers were investigated with differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction measurements. The influence of the content of the crosslinking unit on the phase behavior of the elastomers was examined. Monomer M₁ showed a cholesteric phase, and M₂ displayed smectic and nematic phases. The elastomers containing <15 mol % of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3315–3323, 2005     

Polymeric liquid crystals: structural basis for ferroelectric and nonlinear optical properties

This paper describes the rational design and structure–property relations in three different types of polar LC polymers with interesting material properties, as follows. (i) Chiral LC polymers, which are functionalized with crosslinkable groups, can be converted into LC elastomers with chiral smectic C^* phases. The mechanical orientability of these elastomers leads to new piezoelectric materials. (ii) The curing (dense crosslinking) of a polymer matrix provides one possibility of stabilizing the polar order of dye molecules, which is necessary for frequency doubling. Additionally, LC phases can help to stabilize this polar structure, which leads to large and stable nonlinear optical coefficients. (iii) Polymer analogous esterifications offer a convenient method for the synthesis of chiral smectic C^* polymers with large ferrolectric polarizations.     

Mesomorphic properties of side-chain cholesteric liquid-crystalline elastomers

New monomer cholesteryl 4-(10-undecylen-1-yloxybenzoyloxy)-4′-ethoxybenzoate (M₁), crosslinking agent biphenyl 4,4′-bis(10-undecylen-1-yloxybenzoyloxy-p-ethoxybenzoate) (M₂) and a series of side-chain cholesteric elastomers were prepared. The chemical structures of the monomers and elastomers obtained were confirmed by element analyses, FT-IR, and ¹H NMR. The mesomorphic properties and thermal stability were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction measurements. The influence of the content of the crosslinking unit on the phase behavior of the elastomers was examined. M ₁ showed cholesteric phase, and M ₂ displayed nematic phase. The elastomers containing less than 12 mol% of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability.     

Synthesis and characterization of two series of pressure-sensitive cholesteric liquid crystal elastomers with optical properties

ABSTRACT

We synthesized two series of cholesteric liquid-crystal elastomers by hydrosilylation among monomers MA containing a cholesteryl group, MB (MC) containing a phenolic hydroxyl group and MD as the crosslinker. The chemical structures of all the monomers and LCEs were confirmed by ¹H NMR and FT-IR. We explored the mesomorphic properties and phase behaviours by TGA, DSC, POM, and XRD. All the LCEs presented elasticity, reversible phase transition, and high thermal stability. For two series of LCEs, the glass transition temperature increased slowly, and the isotropic transition temperature increased obviously. PA-I-PA-V and PB-I-PB-IV displayed selective reflection and colourful Grandjean texture, but PA-VI, PB-V, and PB-VI needed external pressure to show them.     

Side-chain cholesteric liquid crystalline elastomers derived from a mesogenic crosslinking agent: I. Synthesis and mesomorphic properties

The synthesis of new side-chain cholesteric elastomers derived from a cholesteric monomer and mesogenic crosslinking agent is presented. The chemical structures of the monomers obtained were confirmed by elemental analyses, FT-IR, ¹H NMR, and ¹³C NMR. The mesomorphic properties and thermal stability were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarizing optical microscopy (POM), and X-ray diffraction (XRD) measurements. M₁ showed cholesteric phase, and M₂ displayed enantiotropic nematic phase and monotropic smectic phase. The elastomers containing less than 12 mol% of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability.     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4'-allyloxybiphenyl 4'-ethoxybenzoate, M₁), a chiral crosslinking agent (isosorbide 4-allyloxybenzoyl bisate, M₂) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂. The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X-ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂-P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145-209.6°C, with no changed on the cooling. Polymers P₄-P₇, with more than 6 mol % of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15 mol % of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

Chiral nematic phase in hydrogen-bonded blends of a side-chain smectic polymer with low molar mass dopants

The possibility of chiral nematic mesophase induction in blends of a smectic A side-chain liquid-crystalline copolymer with low molar mass dopants was studied. The chirality of the initial copolymer was determined by the cholesterol optical active groups; however, in the individual state it was not able to form any chiral liquid-crystalline phases. We have shown that the induction of the chiral nematic phase becomes possible in blends of such a copolymer with low molar mass dopants that are stabilized by hydrogen bonding. Phase behavior and optical properties of the blends were studied with X-ray scattering, differential scanning calorimetry and polarizing microscopy. Owing to hydrogen bonding the blends are stable over a wide range of contents and temperatures. The nature of the end group in the dopant molecules is shown to have an important influence on the chiral mesophase induction concentration and the clearing temperatures of the blends. Temperature and concentration dependences of the selective reflection maximum wavelength in the chiral nematic phase were also studied.

A chiral cobaltous complex with acetone <Emphasis Type="Italic">S</Emphasis>-1,1′-binaphtyl-2,2′-diimine

Crystallization of cobalt(II) chloride and S-(?)-1,1′-binaphtyl-2,2′-diamine (L) from an acetone solution has afforded a chiral complex [CoL^*Cl₂]·Me₂CO (L^* = the acetone diimine derivative of binaphtyldiamine). The compound has been structurally characterized.     

Synthesis and properties of side-chain liquid crystalline polymers grafted with chiral dimers containing cholesteryl groups

ABSTRACT

Two series of novel side-chain liquid crystal (LC) polysiloxanes grafted with chiral liquid crystalline dimers containing cholesteryl mesogens were synthesised. The chemical structure and LC properties of comonomers and polymers were characterised by FTIR, ¹H-NMR, DSC, TGA, POM and XRD. M₁ and M₂ were chiral nematic (N*) dimers, and M₃ was an achiral LC monomer displaying nematic mesophase in a narrow mesomorphic temperature range, while the copolymers exhibited N* mesophase whose mesomorphic temperature ranges were much wider than those of the comonomers. Moreover, the glass transition temperatures and isotropization temperatures of the polymers all decreased with decreasing the dimer components. Reflection spectra showed that P_a series tend to attain wide-band selective reflection at long wavelengths, while P_b series were more potential at short wavelengths with narrow bandwidths. Decreasing the dimer components led the wavelength of the selective reflection to blue shift, which was an abnormal phenomenon in chiral mixture system.     

The thermotropic and lyotropic liquid-crystalline properties of acetoacetoxypropyl cellulose

Acetoacetoxypropyl cellulose, formed by the acetoacetylation of hydroxypropyl cellulose using a diketene/acetone adduct at elevated temperature, forms both thermotropic and lyotropic liquid-crystalline phases. DSC and hot-stage polarized light microscopy confirmed the thermotropic nature of the bulk polymer. Thin layers showed green reflection colors at room temperature. The wavelength λ₀ of selective reflection was measured spectrophotometrically. The crystalline structure of the polymer was investigated using x-ray diffraction. A lyotropic mesophase formed in acetic acid at ≥ 40 wt% polymer. The value of λ₀ for the lyotropic cholesteric mesophase was determined by optical rotatory dispersion (ORD) and circular dichroism (CD) of a thin layer of a wholly anisotropic solution.