Fan-Bao Meng

Liquid-crystalline elastomers produced by chemical crosslinking agents containing sulfonic acid groups

Abstract A series of siloxane-based liquid-crystalline (LC) elastomers were synthesized by using chemical crosslinking agents containing sulfonic acid groups. The crosslink densities of the elastomers were determined by swelling experiments. Two kinds of melting temperature corresponding to crystallization of siloxane matrix and crystallization of LC segments were clearly detected. Some of the polymers exhibited smectic mesophase textures or cholesteric mesophase textures. A proposed model containing LC segment structure and ionic crosslinking lamellar structure separated by siloxane chains was given. The ion aggregated in domains forces the siloxane chains to fold and form an irregular lamellar structure. Ionic aggregates and LC segments may be dispersed each other to form multiple blocks with increasing ionic crosslinking content.

Synthesis and characterization of side chain liquid crystalline polymers exhibiting cholesteric and blue phases

A series of cyclosiloxane‐based cholesteric liquid crystalline (LC) polymers were synthesized from a cholesteric LC monomer cholest‐5‐en‐3‐yl(3β) 4‐(2‐propenyloxy)benzoate and a nematic LC monomer butyl 4‐[4‐(2‐propenyloxy)benzoxy]benzoate. All the polymers exhibit thermotropic LC properties and show cholesteric phases. Most of the polymers display four types of phase transition behaviour corresponding to glass transition, melting point, cholesteric phase–blue phase transition and clearing point. The mesophase temperature range of the blue phases are as broad as 20°C. The blue phase was confirmed by the apperance of planar textures and cubic packings. With an increase of non‐chiral component in the polymers, the clearing point decreases slightly, while the glass transition and melting temperatures change little. In the reflection spectra of the polymer series the reflected wavelength broadens and shifts to longer wavelength with increase of the non‐chiral component in the polymer systems, suggesting that the helical pitch P lengthens.

Liquid-crystalline behaviours of novel chitosan derivates containing singular and cholesteryl groups

A series of esters of chitosan with cholesteryl hexanoate and cholesteryl decanoate side chains were synthesised. These compounds had higher solubilities than chitosan itself and all formed cholesteric lyotropic liquid crystalline phases. They had enhanced mesogenic properties as compared with the parent polymer. We consider that these compounds may prove to be of value as vehicles for drug delivery.

Synthesis and characterisation of imidazolium-based ionic liquid crystals bearing a cholesteryl mesogenic group

A series of cholesteryl-containing imidazolium chlorides and imidazolium tetrachloroaluminates were synthesised, and the chemical structure, liquid crystalline behaviour and ionic conductivity were characterised by several technical methods. Whereas the imidazolium chlorides show chiral smectic A (SmA*) phase on heating and cooling cycles, the imidazolium tetrachloroaluminates display chiral nematic (N*) phase, which is uncommon for ionic liquid crystals (ILCs). The imidazolium chlorides display similar phase transition temperature and entropy, indicating the cholesteryl component influence predominately on the phase transition rather than the different alkyl substituent groups. The imidazolium tetrachloroaluminates show lower melting point temperatures and lower clear point temperature than the imidazolium chlorides. The mesophases exist at rather moderate temperatures. Non-mesomorphic imidazolium tetrachloroaluminate(III) salts with short alkyl substituents have been known for a long time, and the synthesised imidazolium tetrachloroaluminates are the first examples of tetrahalogenoaluminate(III)-containing ILCs. For the imidazolium tetrachloroaluminates, imidazolium cations combine loosely with AlCl4− ions because AlCl4− ions are large and occupy more space in spite of the hydrogen bond and electrostatic attraction interaction, indicating that the layer structure can be destroyed easily to form N* phase on heating.

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 MC(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 (Td) were greater than 310°C for all the polymers.

Synthesis and mesomorphic behaviour of novel chiral nematic side chain liquid crystalline polysiloxanes

A series of novel thermotropic side chain liquid crystalline polymers was synthesized by grafting copolymerization of a mesogenic monomer, 4-allyloxybenzoyl-4′ -(4-n-alkylbenzoyl)–p-benzenediol bisate and a chiral monomer, menthyl undecylenate. The mesogenic monomers exhibited nematic threadlike textures during heating and cooling. The polymers showed thermotropic liquid crystalline properties with a broad mesomorphic region over a range of 100°C. The polymers exhibited a cholesteric mesophase with a colourful Grand-Jean texture when the content of chiral units was greater than 15 mol %; the others exhibited nematic threadlike textures. All of the polymers were thermally stable over 300°C, and most were laevorotatory as the chiral monomer.

Synthesis and characterization of imidazolium-based polymerized ionic liquid crystals containing cholesteryl mesogens

A series of polymerized ionic liquid crystals (PILCs) with different anions were synthesized and characterized, including bromides (PIBs), tetrafluoroborates (PITs), hexafluorophosphates (PIHs), trifluoromethanesulfonates (PITFs), and bis(trifluoromethylsulfonyl)imides (PIBTs). The PIBs show both smectic A (SmA) phase and chiral nematic (N*) mesophases on heating and cooling cycles, but other PILCs exhibit only chiral nematic mesophase. The glass transition temperature (Tg) of the PIBs, PIHs, PITs, PITFs, and PIBTs decreases successively, but the isotropic temperature (Ti) shows no big change. All these PILCs display ionic conductivity in mesophase. The PITs present a little higher ionic conductivity than other PILCs indicating that the ionic conductivities of these PILCs depend on the nature of the anions. The molecular packing of these PILCs is distinct from each other due to different anions. The bromides (PIBs) should form intimate ion pairs, but other PILCs should form ion clusters rather than ion pairs due to large size of anions.

The effect of different arms on the properties of chiral branched-arm liquid crystals based on isosorbide as the chiral core

A new series of two-arm ( MA1 , MA2 ), four-arm ( MA3 ) and six-arm ( MA4 ) chiral liquid crystalline compounds containing isosorbide as the chiral core were synthesised. Four precursors of branched-arm A1–A4 were first obtained, and then were esterised separately with isosorbide to obtain four chiral branched-arm liquid crystals ( MA1–MA4 ). The structure and properties have been characterised. The results show that MA1 was smectic–cholesteric phase with a fan-like and oily streak texture; MA2–MA4 showed a cholesteric phase with oily streak texture, or lined texture and finger print texture. Isosorbide successfully induced a cholesteric phase. The melting point and clearing point values for MA1–MA4 first increased and then decreased. The branched-arm and chiral core quantity affected the liquid crystalline properties. At the same time, the difference in side-arms resulted in different directions of rotation. MA1–MA2 showed right-handed rotation and had selective reflection; MA3–MA4 demonstrated left-handed rotation and did not have selective reflection.

Effect of ionic aggregates of sulphonate groups on the liquid crystalline behaviours of liquid crystalline elastomers

A series of siloxane‐based liquid crystalline elastomers containing biphenyl benzoate mesogenic units and ionic Brilliant Yellow moieties was synthesized. The chemical structures and liquid crystalline properties of the samples were characterized by FTIR, 1H NMR, DSC, POM and XRD. The effective crosslink density of the ionic elastomers was determined by swelling experiments in organic/buffer mixtures. All the polymers displayed a smectic mesophase. It was shown that the glass transition and melting point temperatures of the polymers increased slightly with increasing content of ionic and mesogenic groups in the polymers, while the liquid crystal mesophase region decrease slightly.

Polymerised ionic liquid crystals bearing imidazolium and bipyridinium groups

ABSTRACT Novel kinds of polymerised ionic liquid crystals (PILCs) bearing imidazolium and bipyridinium groups were synthesised and characterised in this work. Some bromo-polyesters were synthesised in an esterification chain reaction using 2,3-dibromosuccinyl dichloride, isophthaloyl chloride and 4,4′-biphenol. The polyester imidazolium bromides (PIBs) and polyester dipyridinium bromides (PDBs) were obtained by a quaternisation reaction between the bromo-polyesters, N-methylimidazole and 4-4′-bipyridine, respectively. The polyester imidazolium tetrafluoroborates (PITs) and polyester dipyridinium tetrafluoroborates (PDTs) were synthesised using the corresponding PIBs and PDBs in an anion-exchange reaction. The chemical structures, liquid crystalline properties and molecular weights of these polymers were characterised by multiple experimental techniques. All the PILCs including PIBs, PDBs, PITs and PDTs display smectic A phase on heating and cooling cycles. The liquid-crystalline properties of bromo-polyesters are influenced by the length of flexible spacer and composition of polyester backbones, while those of PILCs are determined by the ionic groups as additional important influent factors. In comparison with those of the mother bromo-polyesters, the d-spacing of PILCs reduced slightly due to Im+–Br−, Dp+–Br−, Im+–BF4− and Dp+–BF4− ion pairs in the polymer systems. Monocationic imidazolium salts display weaker interionic and intermolecular interaction, higher mobility and lower viscosity than dicationic dipyridinium salts. GRAPHICAL ABSTRACT