Liquid-crystalline polyesters based on branched propylene spacers

A new promising concept of spacer modification in main chain liquid crystalline polymers is the use of branched alkylene spacers. In this article we give as a first example the polyesters of p, p′-terphenyl-4,4′-dicarboxylic acid as mesogenic unit and disubstituted propylene spacers. The steric restrictions of the spacers lower the melting points compared with the polyesters with linear spacer but they do not flexibilize the main chains as linear alkylspacers do. This leads to a residual stability range of the liquid crystalline state in the homologues of polyesters with disubstituted spacer. The melting and clearing points are lowered to the same extent. Because of the solubility of the higher homologues in common solvents it is possible for the first time to determine molecular masses of this polymer class based on p, p′-terphenyl-4,4′-dicarboxylic acid and aliphatic diols more exactly. X-ray scattering indicates that long side chains are arranged parallel to the main chain and have no longer influence on transition temperatures and intermolecular distances. © 1996 John Wiley & Sons, Inc.     

Thermotropic liquid crystal polyesters derived from 4,4′-biphenyldicarboxylic acid and oxyalkylene spacers

Several polyesters derived from bibenzoic acid and oxyalkylene glycols have been prepared and the ability of formation of mesophases was studied. The phase behaviour was investigated by means of differential scanning calorimetry, wide-angle X-ray diffraction and real-time variable-temperature small-angle X-ray diffraction. A common feature of all the studied polyesters, with ether groups in the spacer, is the inhibited ability for developing three-dimensional structures, in contrast to the polymers with all-methylene spacers. Moreover, the latter polymers show a monotropic mesophase behaviour but the former exhibit an enantiotropic transformation. Smectic structures of different types have been detected: The polyester derived from 3,3'-oxybis(1-propanol) produces a smectic S_A structure, while the polyester from triethylene glycol leads to a smectic S_C mesophase. The influence of the spacers on the dynamic mechanical relaxations of these polybibenzoates has been studied and discussed.     

Fluorocarbon polymers with alternating oxyalkylene and oxysilylene units

Linear polymers were prepared by the condensation of bis(dimethylamino)dimethylsilane and 1,4-bis(dimethylaminodimethylsily)benzene with fluorocarbon diols. 1,5-Dihydroxy-3-methyl-1,1,5,5-tetrakis(trifluoromethyl)-2-pentene, the cis addition product of hexafluoroacetone and isobutylene, with the silylbenzene monomer gave a polymer that cured at room temperature to a rubber exhibiting a glass transition temperature of 0°C, low swelling in hydrocarbons, and excellent resistance to hydrolytic, oxidative, and thermal degradation, retaining its flexibility after exposure to air for 3 hr at 305°C. The polymers obtained by condensing 1,5-dihydroxy-1,1,5,5-tetrakis(trifluoromethyl)-2-pentene, the trans addition product of hexafluoroacetone and propylene, with the silylbenzene and the silane monomers had glass transition temperatures of ?12 and ?50°C respectively, and greater resistance to swelling in hydrocarbons.     

Liquid-crystalline main chain polyesters derived from p-phenylenediacrylic acid

4,4′-(p-phenylenediacryloyloxy)-dibenzoyl chloride was polycondensed at 220°C with several diols in order to obtain liquid-crystalline polymers. The mesomorphic properties were studied by optical microscopy and differential scanning calorimetry. Gelation due to thermal crosslinking occurred at higher temperatures. With the exception of 2,2′-biphenyldiol derivative, all the polymers derived from aliphatic diols, dihydroxy ethers and aromatic diphenols exhibit mesogenic behaviour.     

Liquid crystallinity,IR analysis,and mechanical properties of thermotropic polyamides having alkylene spacers

Thermotropic polyamides with high molecular weights were synthesized by melt polycondensation of 3,3′-disubstituted-4,4′-biphenylenediacetamides with α,o-diphenoxyalkane-4,4′-dicarboxylic acids. Methyl, methoxy, and chloro groups were used as 3,3′-substituents. IR measurements revealed that there are hydrogen-bonded carbonyls and free carbonyls the intensities of which depended on the polymer structure and the temperature. The thermotropic liquid crystallinity of the polyamides is assumed to occur by a decrease in intermolecular hydrogen bondings between carbonyls and amide NH's which was caused both with 3,3′-substitutions of the biphenylene moiety and with introduction of long alkylene spacers in the polymer backbone. In addition, mechanical properties of the thermotropic polyamides were measured on the molded dumbbell-type specimen. The 3,3′-dichloro polyamides showed medium tensile strengths and moduli in the range of 500–890 kgf/cm²a nd 19.0 × 10³ to 27.0 × 10³ kgf/cm², respectively. © 1996 John Wiley & Sons, Inc.     

Linear polyesters containing isocyanurate rings

Two series of linear polyesters containing isocyanurate rings have been prepared to determine the effect of structural variations on thermal and solubility properties. The polyesters were prepared by the polycondensation reaction of isocyanurate containing difunctional acid and ester monomers with linear diols. The substituent on the isocyanurate ring and the length of the acid side chain have been shown to have considerable effect on the glass transition temperature T_g. Different solubility properties were observed for the series of polyesters in which the pendant substituent was ? C₆H₅ and the acid side-chain was ? CH₂CO₂H. These polymers were insoluble in THF, and the polyester prepared from 1,6-hexanediol was also insoluble in chloroform. Thermal gravimetric analysis (TGA) indicated that structural differences had no significant effect on the thermal stability of these linear polyesters.     

Blue light‐emitting poly(p‐phenylenevinylene) derivatives containing alternating conjugated segments and aliphatic spacers

Two new poly(p‐phenylenevinylene) derivatives were prepared by Heck coupling. They contained alternating conjugated segments on the basis of p‐distyrylbenzene and flexible nonconjugated spacers. The synthesized polymers P1 and P2 carried two m‐terphenyl of four tertbutyl pendants, respectively, per repeat unit. Both polymers were amorphous and exhibited satisfactory thermal stability. Polymer P1 displayed a limited solubility in common organic solvents, whereas P2 dissolved readily in these solvents. The glass‐transition temperature values were 128 °C for P1 and 37 °C for P2 . The polymers emitted blue or violet‐blue light with photoluminescent maxima at about 445 and 460 nm for solutions and thin films, respectively. The bulky pendants reduced their tendency to form aggregates. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1091–1098, 2003     

Conformational structure of liquid-crystalline polyesters with mesogens and spacers in the main chain

The conformations of thermotropic polyesters with alternating mesogens and poly(methylene) spacers in the main chain were investigated by conformational calculations using the data of linear-dichroism IR-spectroscopy, X-ray analysis and differential scanning calorimetry. The conformations of monomeric units and of the macromolecules as a whole in different phase-aggregated states were estimated. It is shown that in the liquid-crystalline (LC) state the polymer chains are strongly extended. The results are compared with the data of various theories of LC ordering.     

The influence of alkylene spacers on conformational and thermal properties of poly (aryl methacrylates)

The effect of introducing alkylene spacers on the thermal and conformational properties of poly(aryl methacrylates) has been studied. Poly(2-phenylethyl-1-methacrylate) (PPEMA) and poly(4-phenylbutyl-1-methacrylate) (PPBMA) samples of narrow poly-dispersities and covering a very broad range of molecular weights were produced by free radical solution polymerization, followed by fractionation. These materials were studied by a combination of differential scanning calorimetry, light scattering, and viscometry measurements to allow evaluation of their glass transition temperatures (T_g) and characteristic ratios (C_∞). These results are compared with literature data available for poly(phenyl methacrylate) (PPMA), which has no alkylene spacer, and poly(benzylmethacrylate) (PBMA), which has a methylene spacer. A progressive decrease in T_g is observed as the length of the alkylene spacer is increased, reflecting the enhancement of side group (local) flexibility. C_∞ decreases substantially on going from PPMA to PBMA but then increases on going to PPEMA and PPBMA. This behavior is attributed to the fact that while side group flexibility increases for the materials with longer alkylene spacers, and this would be expected to decrease C_∞, the side group size is progressively increasing. Larger side groups generally increase C_∞ of polymethacrylates. Thus the observed C_∞ behavior for these polymers reflects both the size and flexibility of the substituents. © 1994 John Wiley & Sons, Inc.     

Synthesis and characterization of liquid–crystalline polyesters with chiral and achiral twin spacers

A series of novel thermotropic main-chain chiral liquid–crystalline random copolyesters consisting of spacers of two different types—chiral and achiral—was synthesized. Polyesters (BmTa) with tartaric acid as the chiral spacer (Ta), aliphatic diols (with ‘m’ = 2–10 methylene groups) as the achiral spacers, and 4,4′-dihydroxy biphenyl (B) as the mesogen were synthesized via condensation polymerization in solution after duly protecting the 2,3-dihydroxy groups of tartaric acid by acetylation. The copolymers were characterized by Fourier transform infrared spectroscopy, ¹H and ¹³C NMR spectra, gel permeation chromatography, and thermogravimetric analysis. Transition temperatures for phase changes recorded by DSC were corroborated with the textures observed by a hot-stage optical polarizing microscope. The wide-angle X-ray diffraction (WAXD) profiles indicated a SmE phase at room temperature. The lower angle region at 2θ = 0.5–2.45 covered by WAXD indicated a layer of thickness of 161 Å, less than the molecular length for B0Ta. The [α_D] values were recorded on a digital polarimeter. The birefringence was lost at higher mesophase temperatures in lower members with m < 5, a behavior found in certain chiral systems, and the higher members with m > 5 showed a lesser number of phase transitions. On cooling, the polyesters produced a texture with the formation of transition bars. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1743–1752, 2001     

Liquid-crystalline monomers, dimers and side group polymers containing phenylpyrimidine mesogens

Phenylpyrimidine derivatives were used to synthesize monomers, dimers and side group polymers. Only a few monomers and dimers show liquid-crystalline behaviour whereas almost all of the polysiloxanes, polyacrylates and polymetha-crylates prepared possess enantiotropic Hquid-crystalline phases. The structure of the main chain and of the mesogenic unit as well as the length of the spacer and of the terminal groups were modified. The relation between structure and phase behaviour is discussed.     

Antimicrobial polyesters containing Schiff-base metal complexes

Antimicrobial polyesters containing Schiff-base metal complexes (PSB) were prepared by polycondensation of adipoyl chloride with chelated Schiff-base diol {bis-(2-hydroxy-5-methylol-benzaldehyde)ethylenediamine}. All the metal chelated polyesters were characterized by elemental analysis, UV–Visible, FTIR, ¹³C and ¹H NMR spectra and thermogravimetric analysis. The analytical data of the polyesters agreed with 1 : 1 molar ratio (metal chelated diols to adipoyl chloride). The geometry of the chelated polyesters was confirmed by magnetic susceptibility measurements and UV–Visible spectroscopy. The thermal behaviors of these chelated polyesters were studied by TGA (Thermogravimetric analyzer) in a nitrogen atmosphere up to 800°C. The TGA results revealed that the Cu(II) chelated polyester has better heat resistant properties than the other polyesters. The antimicrobial properties of these polyesters were investigated with agar diffusion methods against selected microorganisms Bacillus subtelillis, Bacillus megaterium, Streptococcus aureus, Escherichia coli, Salmonella typhi, Pseudomonas aeruginosa, Shigella boydii and for antifungal activity against Candida albicans, Trichophyton longifusus, Aspergillus flavus, Aspergillus niger, Fusarium solani, Microsporum canis, Puccinia graminis. The antimicrobial activity of these polyesters was higher than standard drugs Kanamycin and Miconazol.     

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 of arylenealkyne conjugated macrocycles containing a long alkylene bridge

The synthesis of the first two arylenealkyne conjugated macrocycles containing a long alkylene bridge via Glaser coupling of template-directed tetraacetylenes was reported. Tetraacetylene intermediates with complex structures were constructed rapidly via quadruple Hagihara coupling of monoprotected bisacetylenes to appropriate tetraiodides and subsequent desilylation. The characterization of such compounds was carried out by NMR, GPC and UV-Vis spectra. Unfortunately, the two compounds were not liquid crystals and had no biaxial nematic mesophase character as expected. __________ Translated from Chemical Journal of Chinese Universities, 2007, 28(1): 65–70 [译自: 高等学校化学学报]     

Synthesis and properties of polyesters containing naphthalenetetracarboxylic imide

Poly(ethylene naphthalates) containing small contents of N, N'-bis(ω-hydroxypropyl)naphthalene-1, 4, 5, 8-tetracarboxylic imide(HPNTI) unit as the photostabilizing component, which are stable to ultraviolet lights, were synthesized from dimethyl naphthalate, ethylene glycol, and HPNTI. The polyesters obtained were characterized by fluorescence spectroscopy and measurements of molecular weights and thermal properties.     

Thermal analysis of polyesters containing oxirane groups

The preliminary studies of the thermal behaviour of polyester obtained in polycondensation process of cyclohex-4-ene-1,2-dicarboxylic anhydride and ethylene glycol and its new epoxidized form have been performed. The thermal characterization of initial polyester and its completely oxidized form was done by using differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). The non-isothermal DSC was applied to determine the influence of time and the temperature on the chemical modification of initial polyester using 38-40% solution of peracetic acid. On the basis of DSC profiles it has been found that the endothermic transition, due to the degradation process of initial polyester was characteristic feature under controlled heating program. The two characteristic transitions for the new epoxidized polyester, the exothermic peak corresponded to the thermal crosslinking of epoxidized polyester (322.8–336.4°C) and the endothermic decomposition peak of the cured material (363.8–388.9°C) were observed. The peak maximum temperatures (Tmax) and the heat of cross-linking reaction (ΔH_c) for epoxypolyester prepared at 20–60°C under 1–4 h were evaluated. The Tmax1 were almost independent from epoxidation conditions, while, the values of ΔH_c were dependent from conditions of synthesis. The ΔH_c values of this process decreased when time of oxidation increased. The highest values of ΔH_c at 40°C were obtained. Additionally, TG experiments confirmed two separated degradation steps of the new epoxidized polyester indicating the ester (370–380°C) and ether (450–460°C) bond breakdown.     

Nematic and cholesteric thermotropic polyesters with azoxybenzene mesogenic units and flexible spacers in the main chain

Properties of linear polyesters based on azoxybenzene and 2,2′-methylazoxybenzene moieties with linear, flexible spacers based on mixtures of dodecanedioic acid (DDA) and methyladipic acid (MAA), chiral or racemic, of various compositions (system MAA/DDA-8 and MAA/DDA-9, respectively) have been described. Substitution of methyl groups in the 2,2′ or 3,3′ positions of the mesogenic core leads to soluble and relatively low-melting-point polyesters. The viscosity law for (MAA/DDA-9) polyesters in 1,1,2,2 tetrachloroethane gives an exponent 0.76, indicating well-sol-vated, coiled chain conformations in dilute solution. Calorimetric data show an increase in isotropization entropy ΔS_NI with increasing average length of the spacer. This suggests a nonrandom conformation of the spacer in the nematic melt with a degree of order superior to that of low-molecular-weight analogs. X-ray data obtained with an oriented nematic glass quenched from the nematic melt of DDA-9 subjected to a magnetic field of 10–12 T also support the extended-chain model in the nematic phase of DDA-9. Oriented fibers can be produced by subjecting nematic melts of polyesters 8 and 9 either to magnetic fields of high intensity or to shear fields. The x-ray data obtained from these fibers also support the extended-chain model. Cholesteric systems do not orient in the magnetic field of 10–12 T. The study of mesophases of systems 8 and 9 indicates a dramatic influence of the position of the ester group on the stability of the mesophase in the azoxybenzene polyesters. The results are interpreted in terms of geometric factors influencing the colinearity of the mesogenic core and of the extended spacer.     

Synthesis and characterization of polyesters containing heterocyclic thiaxanthone units

Several polyesters containing thiaxanthone rings were prepared from 2,7-dichloroformylthiaxanthone-5,5′-dioxide ( IVa ), 2,8-dichloroformylthiaxanthone-5,5′-dioxide ( IVb ), and bisphenols by solution polycondensation. The 2,8-diethoxycarbonylthiaxanthone-5,5′-dioxide ( V ) was prepared and characterized by spectral methods to confirm the formation of 2,8-thiaxanthonedicarboxylic acid-5,5′-dioxide ( IVb ). Prior to polymer synthesis two model compounds,2,7-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-1) and 2,8-diphenoxycarbonylthiaxanthone-5,5′-dioxide (MDE-2), were synthesized and characterized by spectral methods. The polyesters were obtained in 62–78% yield and had inherent viscosities in the range 0.42–0.90 dL/g. The effect of thiaxanthone rings on solubility, crystallinity, and thermal stability of the polyesters are also discussed. The polyesters have decomposition temperatures in the range 372–438°C.     

Liquid crystal polymers. IV. Thermotropic polyesters with flexible spacers in the main chain

Two closely related series of polyesters that contain mesogenic units interconnected by flexible spacers along the main chain were prepared and characterized for their liquid crystal properties. All of these polymers showed theotropic behavior, which was examined by DSC, hot-stage microscopy on a polarizing microscope, small-angle light and wide-angle x-ray scattering methods, and visual observation of stir-opalescence of the polymer melts. The effect of the length of the flexible spacer and the nature of the substituent, which is on the central aromatic ring of the mesogenic unit, on the stability and molecular order of the mesophase for each of the polymers was investigated and the results are discussed on the basis of the thermodynamic data obtained.     

Synthesis and characterization of new ferroelectric liquid crystals containing oligomethylene spacers

Two series of ferroelectric liquid crystals containing a phenyl biphenyl carboxylate mesogenic group and oligomethylene spacers (n 3, 4, 6, 8) were synthesized and characterized. The chiral moieties are the (S)-2-methylbutoxycarbonyl and (S)-1-methylheptoxycarbonyl groups. The mesomorphic behaviours of the compounds were characterized using differential scanning calorimetry and optical polarized microscopy. Spontaneous polarization (P) of the liquid crystals was measured by an automated polarization tester over a wide temperature range. The mesomorphic properties are discussed as a function of spacer length and position of the chiral centre. It is found that the phase transition temperature decreases with increasing number of oligomethylene units. The phase behaviours of the LC with (S)-1-methylheptoxycarbonyl are more complex than those with (S)-2-methylbutoxycarbonyl, due to the flexible tail in the former. Moreover, the spontaneous polarization depends mainly on the position of the chiral centre, with Ps 15 nC cm 2 and Ps 60 123 nC cm 2 for the series s with (S)-2-methylbutoxycarbonyl and (S)-1-methylheptoxycarbonyl groups, respectively.