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.     

Synthesis and characterization of fluorine-containing cholesteric liquid crystalline polysiloxanes bearing trifluoromethyl-substituted mesogens

A series of side-chain liquid crystal (LC) polysiloxanes were synthesised with Poly(methylhydrogeno)siloxane, 4?-(undec-10-enoyloxy) biphenyl – 4 – yl 4- (trifluoromethyl) benzoate (M_th) and a chiral nematic (N*) LC monomer 1-allyl 10-(cholesteryl)-decanedioate (M_ch). The chemical structures and LC properties of the monomers and polymers were characterised by FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analysis, POM and X-ray diffractometer. M_ch is monotropic N* LC. The homopolymer derived from monomer M_ch is enantiotropic N* LC. Monomer M_th is a smectic A liquid crystal. The copolymers derived from M_ch and M_th are N* LCs. The temperatures at which 5% weight loss occurred are greater than 300°C for all the fluoro-containing polymers, and the residue weights of the samples at 600°C increased slightly as the content of trifluoromethyl mesogens increased in the polymers. The glass transition temperatures of the polymers increased as trifluoromethyl mesogens increased, too. The N*–I phase transition temperatures show a negative deviate from ideal or linear behaviour. The values of the enthalpy changes for the cholesteryl containing polymers are rather low and this is attributed to the biaxiality of cholesteryl moiety which tends to reduce the change in the orientational order at the N*–I transition. Compared to the monomers, the polymers show wider mesophase region.     

New side chain cholesterol-functionalised aliphatic polycarbonate copolymer: synthesis and phase behaviour

A new side cholesterol-functionalised liquid crystal (LC) copolymer based on aliphatic polycarbonate backbone was synthesised. The chemical structures of the block copolymers obtained in this study were characterised with Fourier Transform Infrared Spectroscopy (FT-IR) and Proton Nuclear Magnetic Resonance (¹H NMR) spectra. Their thermal stability and phase behaviours were investigated with thermogravimetric analysis (TGA) measurements, differential scanning calorimetry, and polarising optical microscopy. The molecular organisation in the mesophase was studied by temperature-dependent X-ray diffraction (XRD). As a result, the block copolymer bearing side cholesteryl groups showed a glass transition at 15.8°C and a smectic A (SmA) to isotropic phase transition at 151.3°C on heating cycle. XRD indicated that the block LC copolymer showed an interdigitated molecular arrangement of the mesogenic units within the smectic layers. This partial bilayer structure was similar to the SmA phase formed by polar mesogens.     

In situ control of surface molecular order in liquid crystals using a localised polymer network and its application to electro-optical devices

A liquid crystal (LC) alignment technique has been developed that allows local control of the polar pretilt angle over the range of 0–90°. This was achieved through the formation of a polymer network localised in the vicinity of the LC cell substrates. The network was formed as a result of in situ UV-induced polymerisation of a photo-reactive monomer added at concentrations of 0.5–1%. Localisation of the polymer network at the LC–substrate boundary was achieved by the application of a high voltage before polymerisation. The resultant pretilt angle was determined by the voltage applied during the polymerisation and/or the duration of the voltage application before the polymerisation step. The desired pretilt angle could be set over a small area of the sample, which allows the fabrication of LC devices with spatially variable optical retardation. Using this method we fabricated a converging lens, a bi-prism, and a phase diffraction grating with resolution greater than 50 lines mm^?1.     

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.     

Benzoxazine-epoxy thermosets with smectic phase structures for high thermal conductive materials

ABSTRACT

To further increase the intrinsic thermal conductivity (TC) of polybenzoxazine, a series of benzoxazine-epoxy thermosets (s-PBEI) were obtained through the sequential curing of a smectic phase epoxy monomer (s-EP) and a bifunctional benzoxazine monomer (BZ) in the presence of imidazole. The results show that s-PBEI exhibits a smectic mesophase. The formation mechanism of the smectic phase is reaction-induced phase separation caused by the preferential curing of s-EP. Owing to the increment of the liquid crystalline structure content, the TC of s-PBEI increases with increasing s-EP content. The TC of s-PBEI55 containing equal weight of BZ and s-EP reaches 0.30 W m^?1 K^?1, which is higher than that of n-PBEI55, a benzoxazine-epoxy thermoset with nematic phase structures. Additionally, the TC, glass transition temperature, and 10% weight loss temperature of s-PBEI64 containing 60 wt% BZ and 40 wt% s-EP are 0.28 W m^?1 K^?1, 216°C, and 334°C, respectively, indicating its potential applications in electronic packaging, LED lighting, and other fields requiring a high TC resin matrix.     

Self-assembly of amphiphilic liquid crystal polymers obtained from a cyclopropane-1,1-dicarboxylate bearing a cholesteryl mesogen

We study the self-assembly of a new family of amphiphilic liquid crystal (LC) copolymers synthesized by the anionic ring-opening polymerization of a new cholesterol-based LC monomer, 4-(cholesteryl)butyl ethyl cyclopropane-1,1-dicarboxylate. Using the t-BuP(4) phosphazene base and thiophenol or a poly(ethylene glycol) (PEG) functionalized with thiol group to generate in situ the initiator during the polymerization, LC homopolymer and amphiphilic copolymers with narrow molecular weight distributions were obtained. The self-assemblies of the LC monomer, homopolymer, and block copolymers in bulk and in solution were studied by small-angle X-ray scattering (SAXS), differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and transmission electron microscopy (TEM). All polymers exhibit in bulk an interdigitated smectic A (SmA(d)) phase with a lamellar period of 4.6 nm. The amphiphilic copolymers self-organize in solution into vesicles with wavy membrane and nanoribbons with twisted and folded structures, depending on concentration and size of LC hydrophobic block. These new morphologies will help the comprehension of the fascinating organization of thermotropic mesophase in lyotropic structures.     

Bis allyl benzoxazine: Synthesis, polymerisation and polymer properties

A bis benzoxazine monomer with allyl groups viz: 2,2′-bis (8-allyl-3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) propane (Bz-allyl) was synthesized via a solventless method from 2,2′diallyl bisphenol-A, paraformaldehyde and aniline. The chemical structure of Bz-allyl was confirmed by FTIR, ¹H NMR and ¹³C NMR analyses. The monomer manifested a two-stage thermal polymerisation pattern. The first stage was attributed to the polymerisation of the allyl groups and the second to the ring - opening polymerisation of benzoxazine moiety. The polymerisation profile was investigated with DSC, FT-IR, TGA and pyrolysis-GC techniques. A polymerisation mechanism involving the electrophilic addition of the propagating iminium cation on the aniline ring in lieu of the activated sites of bisphenol-A, (which are blocked by allyl and alkyl substituents) was proposed. Additional cross-linking was provided by thermal addition polymerization of allyl groups. As a result of altered cross-linking via the aniline moiety and the additional cross-linking via allyl groups, the cured polymer exhibited a T_g of ca. 300 °C and high crosslink density. The thermal stability of this polymer was also substantially higher vis-à-vis that of the bisphenol-A based polybenzoxazine. The work focuses on the manipulation of benzoxazine monomer structure to alter the ring-opening polymerisation mechanism and cross-linking to derive polybenzoxazine with improved properties.     

The temperature dependence of nematic liquid crystalline polymer melt diffusion

Abstract

Polymer chain diffusion in the nematic mesophase was studied using a model main chain liquid crystalline (LC) polyether based on 2,2′-dimethyl-4,4′-dihydroxyazoxybenzene and mixed alkane spacers. A side chain LC polymethacrylate containing an azobenzene mesogenic group was also investigated. Tracer diffusion coefficients were determined as a function of temperature by an ion-beam depth profiling technique, forward recoil spectrometry. The results confirm that main chain LC polymer chain dynamics are dramatically affected by phase transitions and sample geometry. This behaviour is in marked contrast to the side chain LC polymer which exhibited no phase dependence on the part of the tracer diffusion coefficient.     

UV-induced vertical alignment liquid crystal cell with two species of monomers having vertical-alignment-induced side-chain group and phenanthrene group

We propose the method for formation of the vertical alignment polymer film by polymerisation of the monomers being dissolved in the liquid crystal (LC) material. For obtaining the vertical alignment, combination of the two monomers, 4-(4?-octyloxy-biphenyl-4-yloxy)-butyl ester (AOBBE) and 2,7-dimethacryloyl-oxy-phenanthrene (DMAPhen), was found to be useful.

The monomer DMAPhen initiates the polymerisation under UV light exposure, and the AOBBE unit induces the vertical alignment without generating any alignment defects. The monomer DMAPhen is useful for maintaining the high voltage holding ratio and low residual direct current voltage after UV light exposure because the molecules of DMAPhen do not remain in the LC layer.     

Novel oxazepinedione-derived symmetric dimers: synthesis and mesophase characterisation of seven-membered heterocyclic compounds

The synthesis and characterisation of three sets of symmetric dimeric compounds composed of seven-membered oxazepinedione heterocyclic rings were carried out. All the dimers possess the tetradecyl- (n = 14) alkyl side chain attached to the nitrogen atom of the oxazepinedione core. The oxazepinedione core in turn was connected with varied connecting spacers (n = 4, 6, 8, 10 and 12). The dimers were spectroscopically characterised by FT-IR, ¹H-NMR, ¹³C-NMR and elemental analysis techniques. The compounds were investigated for liquid crystalline properties using differential scanning calorimetry and polarising optical microscopy with heating assembly. The precursor imines 2a–e itself started exhibiting liquid crystalline SmA/tilted hexatic mesophase. Further fusion of 2a–e with maleic anhydride, succinic anhydride and phthalic anhydride gave the novel oxazepinedione-derived symmetric dimers 3a–e, 4a–e and 5a–e respectively. The dimers 3a–e and 4a–e did not exhibit any liquid crystal (LC) properties. However, the phthalic anhydride-fused oxazepinediones 5a–e show monotropic nematic liquid crystalline phase. The results indicate that the formation of mesophase is dependent on the type of fused oxazepinedione ring.     

Cholesteric liquid crystal displays as optical sensors of barbiturate binding

The influence on the optical properties of cholesteric liquid crystal displays (LCDs) was examined for neutral molecule binding by mesogen/receptors in the mesomorphic phase. The motivation was to prepare neutral molecule sensors that use a colour change to signal analyte binding. A receptor that binds barbiturate analytes was modified with two or one cholesteryl groups to yield compounds 2 and 3, respectively. LCDs were prepared by incorporating one of the receptor/mesogen compounds into a cholesteric LC blend along with a potential H‐bonding guest. The optical properties of the LCDs were then determined by measuring the absorbance of the displays. For various LCDs, the colour of the display depended upon several factors: the amount of guest molecule used, the number of cholesteryl side chains on the receptor and the mole concentration of receptor/mesogen in the blend. In particular, complementary host/guest binding of H‐bonding analytes by the bis(cholesteryl) receptor 2 in a cholesteric LCD caused a change of up to +70 nm, which was observed by the naked eye as a blue‐to‐orange colour change. Control experiments confirm that the colour of an LCD is a consequence of molecular recognition in the mesomorphic phase.     

Benzoxazine-bismaleimide blends: Curing and thermal properties

A blend of bisphenol A based benzoxazine (Bz-A) and a bismaleimide (2,2-bis[4(4-maleimidophenoxy) phenyl] propane (BMI), was thermally polymerised in varying proportions and their cure and thermal characteristics were investigated. The differential scanning calorimetric analysis, supplemented by rheology confirmed a lowering of the cure temperature of BMI in the blend implying catalysis of the maleimide polymerisation by benzoxazine. FTIR studies provided evidences for the H-bonding between carbonyl group of BMI and -OH group of polybenzoxazine in the cured matrix. The cured matrix manifested a dual phase behaviour in SEM and DMTA with the minor phase constituted by polybenzoxazine dispersed in an interpenetrating polymer network (IPN) of polybenzoxazine and cured BMI. The IPN possessed improved thermal stability over the constituent polybenzoxazine. A benzoxazine monomer possessing allyl functional groups, 2,2′-bis(8-allyl-3-phenyl-3,4-dihydro-2H-1,3-benzoxazinyl) propane (Bz-allyl) was reactively blended with the same bismaleimide in varying stoichiometric ratios (Bz-allyl/BMI), where the curing involved mainly Alder-ene reaction between allyl- and maleimides groups and ring-opening polymerisation of benzoxazine. The rheological analysis showed the absence of catalytic polymerisation of BMI in this case. The overall processing temperature was lowered in the blend owing to the co-reaction of the two systems to form a single-phase matrix. The cured resins of both Bz-A/BMI and Bz-allyl/BMI blends exhibited better thermal stability than the respective polybenzoxazines. The T_g of the IPN was significantly improved over that of polybenzoxazine (Bz-A). However, the co-reaction resulted in a marginal decrease in the T_g of the system in comparison to the polybenzoxazine (Bz-allyl).     

Main-chain biodegradable liquid crystal derived from cholesteryl derivative end-capped poly(trimethylene carbonate): synthesis and characterisation

Main-chain biodegradable liquid crystal derived from cholesteryl derivative end-capped poly(trimethylene carbonate) was investigated. The novel liquid crystal was synthesised via ring-opening polymerisation of trimethylene carbonate initiated by cholesteryl derivative with an alkyl spacer and end primary hydroxyl group, without any catalyst. The chemical structure of resulting polymers was verified by ¹H NMR. Liquid crystalline properties were validated by X-ray diffraction, differential scanning calorimetry, and polarising optical microscopy. The results showed that all the synthesised polymers Chol-(CH₂)₂-(TMC)_n exhibited mesomorphism in particular temperature ranges because of the introduction of the cholesteryl derivative moiety.     

Synthesis and phase behaviour of new biodegradable liquid crystalline polycarbonate derived from side chain cholesteryl derivative

A new cholesterol side-functionalised polycarbonate was synthesised through a coupling reaction between the terminal carboxyl group of the monomer 6-cholesteroxy-6-oxocaproic acid (COHA) and side hydroxyl group of the polycarbonate (PHTMC). The chemical structures of the intermediate compounds, monomers and polymers obtained in this study were characterised with FT-IR and ¹H NMR spectrum. Their phase behaviour and thermal stability were investigated using polarising optical microscopy, differential scanning calorimetry, X-ray diffraction and thermogravimetric analysis. The monomer COHA showed a cholesteric phase, while the corresponding cholesterol side-functionalised polycarbonate P(TMC-g-COHA) revealed a smectic A phase. This behaviour was attributed to an increased density of the mesogenic units in side chain and hence an ordered organisation into the mesophase. Furthermore, P(TMC-g-COHA) could exhibit a liquid crystalline state below body temperature (≈37°C). This fact indicated it could be used clinically as a self-assemble material with orientational-order mesophase. In addition, P(TMC-g-COHA) had a good thermal stability, the corresponding thermal decomposition temperature was 241°C.     

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.     

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.     

Low temperature polymerization of novel,monotropic liquid crystalline benzoxazines

Cationic ring opening polymerization at a lower temperature range/faster polymerization than ordinary benzoxazine resins has been achieved without added initiators or catalysts via liquid crystalline (LC) benzoxazine resins. Faster polymerization is observed even above the liquid crystal forming temperature. The FTIR spectra show that opening of the oxazine ring occurs even at 110 °C generating phenolic groups that auto‐catalyzed the cationic polymerization of the monomer increasing the rate of polymerization. The newly formed H‐bonds inhibit the formation of LC phases after polymerization. Some of the monomers show nematic LC transitions upon cooling. None of them showed LC transitions during the heating cycle, exhibiting monotropic LC phases. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5871–5881, 2009     

Side chain liquid crystal poly(fumarate)s bearing tolane‐based mesogens

Cyanotolane or fluorotolane mesogens were for the first time introduced into the fumarate monomer under basic conditions. All fumarate monomers undergo radical polymerization in benzene in the presence of dimethyl 2,2′‐azobis(isobutyrate) as an initiator at 60 °C, affording the corresponding poly(fumarate)s with a molecular weight (M_n) of ～ 10⁴ and an exceptionally narrow polydispersity. The phase behaviors of the fumarate monomers and the correspoding poly(fumarate)s were comprehensively investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and X‐ray diffraction (XRD) analysis. For the fumarate monomers, fluorotolane derivatives were prone to form higher‐order liquid crystal phases such as a smectic phase, while cyanotolane derivatives tended to show a wide mesophase temperature range, depending on the alkyl chain spacer length. Very surprisingly, these features dramatically weakened when they were polymerized. The mesophase temperature ranges became narrow and completely disappeared for the poly(fumarate)s with a shorter alkyl chain spacer. A nematic phase representing lower‐order arrangements became a predominant liquid crystal phase for the poly(fumarate) carrying cyanotolane mesogens. Only the poly(fumarate) carrying fluorotolane mesogens with a longer alkyl chain spacer displayed the characteristic XRD patterns of the smectic B phase. The transient photocurrent measurements of the fumarate monomer with cyanotolane mesogens displayed a hole mobility of the order of 10^?4–10^?5 cm² V^?1 s^?1 at room temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5101–5114, 2008     

UV-induced homeotropic orientation of nematic liquid crystals dissolving two species of monomers carrying liquid-crystalline side-chain group and anthracene group

We propose the technique for formation of the polymer orientation film (POF) by polymerisation of the monomers being dissolved in the liquid crystal (LC) material for controlling the orientation of the LC molecules. For obtaining the homeotropic orientation, combination of the two monomers, 4-(4?-octyloxy-biphenyl-4-yloxy)-butyl ester (AOBBE) and 2,7-dimethacryloyl-oxy-anthracene (DMAAnth), was found to be useful. The monomer DMAAnth initiates the polymerisation under ultraviolet (UV) light exposure, and the AOBBE unit induces the homeotropic orientation. The monomer DMAAnth is useful for maintaining the high voltage holding ratio and low residual direct-current voltage after UV light exposure because the molecules of DMAAnth do not remain in the LC layer.