Thermotropic main‐chain liquid‐crystalline photodimerizable poly(vanillylidenealkyloxy alkylphosphate ester)s containing a cyclopentanone moiety

A new class of main‐chain liquid‐crystalline photodimerizable vanillylidene‐containing alkylpolyphosphate esters were synthesized from 2,5‐bis[m‐hydroxyalkyloxy(vanillylidene)] cyclopentanones with various alkylphosphoro‐ dichloridates by solution polycondensation in chloroform at ambient temperature. Their chemical structures were confirmed by FT‐IR, ¹H, ¹³C and ³¹P NMR spectroscopic analysis. Dilute‐solution viscosity values were measured in order to obtain the intrinsic viscosities of the synthesized polymers. Mesogenic properties and phase behavior were investigated by the use of hot‐stage optical polarized microscopy and differential scanning calorimetry. Thermogravimetric analysis revealed that all of the polymers were stable up to 170–230 °C and decomposed with high char yields. The shorter methylene‐chain‐containing polymers did not show a liquid‐crystalline phase, while the longer methylene‐chain‐ containing polymers showed grainy and nematic textures. The T_g, T_m and T_i values of the polymers decreased with increasing flexible methylene chain length in the polymer backbones. The photocrosslinking properties of the polymers were studied by UV light/UV spectroscopy; the crosslinking proceeds via 2π–2π cycloaddition reactions of the vanillylidene exocyclic double bonds of the polymers. The rate of crosslinking was faster for the pendant ethoxy‐containing polymers than that of the pendant methoxy‐containing polymers. Copyright © 2005 Society of Chemical Industry     

Synthesis,characterization and liquid crystalline properties of polyacrylates and polymethacrylates containing aryl ester pendant unit

Aryloxycarbonylphenyl acrylates and methacrylates were prepared by reacting 4‐acryloyloxybenzoyl chloride and 4‐methacryloyloxybenzoyl chloride with different phenols. They were homopolymerized using benzoyl peroxide as the initiator at 65°C in dimethylformamide. The polymers were characterized by IR and ¹H–NMR spectra and size exclusion chromatography. Differential scanning calorimetry and polarizing optical microscopy studies revealed that the phenyl esters of poly(4‐acryloyloxybenzoic acid) and poly(4‐methacryloyloxybenzoic acid) did not show any liquid crystalline properties, but, the para‐aryl–substituted phenyl esters did exhibit mesophase properties in the temperature range of 98–265°C depending on the nature of the aryl substituent. Polymethacrylates exhibit higher T_g, and lower T_m and T_i than the polyacrylates having the same pendant mesogen. Thermogravimetric analyses have shown that the initial decomposition temperatures of the polymers are above 230°C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 465–474, 2000     

Synthesis and characterization of liquid crystalline polymers containing aromatic ester mesogen and a nonmesogenic ferrocene unit in the spacer

A new series of liquid crystalline polymers containing aromatic triad ester mesogen and 1,1′‐disubstituted ferrocene as a nonmesogenic unit along with polymethylene spacer was synthesized. The polymer was synthesized by a room temperature polycondensation reaction between bis(4‐chloroformyl phenyloxy alkyl ferrocene dicarboxylate) and quinol. The alkyl groups have been varied by an even number of methylene groups with a range from two to ten groups. All the polymers were found to possess liquid crystalline properties. The identification of the mesophase is more transparent with an increase in the spacer. The thermal characteristics were studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results reveal that the thermal stability of the polymers was decreased with increasing spacer length. The T_g, T_m, and T_i of the polymers decreased with increasing methylene groups. The incorporation of the ferrocene moiety also has a considerable effect on the glass transition temperature. The char yield of the polymer decreases with an increasing methylene chain length. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3494–3501, 2002     

Thermotropic liquid‐crystalline polyphosphate esters containing phenolphthalein moiety

A new series of thermotropic liquid‐crystalline (LC) polyphosphate esters containing phenolphthalein as a part of their mesogen has been synthesized by a solution polycondensation method. The even‐numbered methylene spacers were varied from 2–10, and ethyl phosphate was used as a phosphorus heterogeneity. Thermal analysis showed that these polymers are stable up to 275–342°C with high char yield. All of the polymers exhibited liquid‐crystalline properties except for Polymers I and VI. Differential scanning calorimetry (DSC) confirmed the mesophase formation of the polymers. The glass transition temperature (T_g) and melting temperature (T_m) of the polymers were considerably low. A polymer containing phenolphthalein alone as a rigid segment with decamethylene spacers was also synthesized, but it did not show birefringent melt properties. These results reveal that phenolphthalein alone cannot act as a mesogen, whereas phenolphthalein phenylester can. Molecular modeling studies and conformational analysis confirmed that the steric hindrance of phenylester and the conjugation effect could explain the promotion of mesogenic behavior by phenolphthalein phenylester. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 194–200, 2004     

Synthesis and characterization of fluorine‐containing liquid crystalline polysiloxanes bearing cholesteryl cinnamate mesogens and trifluoromethyl‐substituted mesogens

Several novel side‐chain liquid crystalline (LC) polysiloxanes bearing cholesteryl cinnamate mesogens and trifluoromethyl‐substituted mesogens were synthesized by a one‐step hydrosilylation reaction with poly(methylhydrogeno)siloxane, a cholesteric LC monomer cholesteryl 3‐(4‐allyloxy‐phenyl)‐acryloate and a fluoro‐containing LC monomer 4‐[2‐(3‐trifluoromethyl‐phenoxy)‐acetoxy]‐phenyl 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, ¹³C‐NMR, TGA, DSC, POM, and XRD. The temperatures at which 5% weight loss occurred were greater than 300°C for all the polymers, and the residue weight near 600°C increased slightly with increase of the trifluoromethyl‐substituted mesogens in the fluorinated polymer systems. The samples containing mainly cholesteryl cinnamate mesogens showed chiral nematic phase when they were heated and cooled, but the samples containing more trifluoromethyl‐substituted mesogens exhibited chiral smectic A mesophase. The glass transition temperature of the series of polymers increased slightly with increase of trifluoromethyl‐substituted mesogens in the polymer systems, but mesophase–isotropic phase transition temperature did not change greatly. In XRD curves, the intensity of sharp reflections at low angle increased with increase of trifluoromethyl‐substituted mesogens in the fluorinated polymers systems, indicating that the smectic order derived from trifluoromethyl‐substituted mesogens should be strengthened. These results should be due to the fluorophobic effect between trifluoromethyl‐substituted mesogens and the polymer matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of α‐methylstilbene‐ and azobenzene‐based thermotropic liquid crystalline polymers

A series of combined liquid crystalline poly(bis‐4,4′‐oxy‐α‐methylstilbene‐4‐substituted (X) phenylazo‐4′‐phenyloxydecylphosphate ester)s bearing photoreactive mesogenic units were synthesized. FTIR and ¹H NMR spectroscopy confirmed the structures of these polymers. The inherent viscosities of the polymers were found to be in the range 0.45–0.65 dL g^?1. Polarizing optical microscopy (POM) exhibited birefringent liquid crystalline melt properties. The thermal properties of all of the polymers were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The photochemical properties of these polymers were studied by UV‐visible and fluorescence spectroscopy. The influence of the photoinduced E–Z (trans–cis) isomerization of the various terminal substituents of the side‐chain azobenzenes was investigated. The kinetics of the photoisomerization process reveal the switching times for the conversion between the trans‐ and cis‐ forms of the azobenzene units. The photo‐optical properties of these polymers exhibited layered smectic phases and showed good photoinduced properties in their mesomorphic states. Copyright © 2005 Society of Chemical Industry     

Studies on the mesomorphic properties of ferrocenylene‐based organophosphorous liquid‐crystalline polymers containing phenyl and biphenyl pendant units

The synthesis, mesomorphic character, and effect of spacers in ferrocene‐containing main‐chain liquid‐crystalline polymers are reported in this article. Two different monomers containing ferrocene and phenyl/biphenyl phosphate groups possessing even numbers of spacers from 2 to 10 were prepared and polymerized by polycondensation at room temperature. All the polymers gave birefringent melt except one. The identification of the mesophase was transparent with an increase in spacers. The effect of substitution in the side chain with regard to bulkiness and spacers were studied with thermogravimetric analysis and differential scanning calorimetry. The results reveal that the thermal stability of the polymers increased with the increasing bulkiness of the side chain and decreased with increasing spacer length. The incorporation of the phosphorous moiety also had a considerable effect on the glass‐transition temperature. Char yield of the polymer decreased with increasing methylene chain length, and it did not vary much with the size of the pendent groups. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 831–841, 2002     

新型硅碳烷液晶树状物的合成与表征--端基含12个己氧基偶氮苯介晶基元

以基于季戊四醇-四烯丙基醚的硅氢化产物PCSi-1G-C1为脚手架、4-己氧基-4′-羟己氧基偶氮苯(M-C6)为介晶基元,合成了季戊四醇为核、端基含12个己氧基偶氮苯的新型硅碳烷液晶树状物PCSi-1G-C6.利用元素分析、傅立叶变换红外光谱(FT-IR)、核磁共振(NMR)、偏光显微镜(POM)和差示扫描量热(DSC)进行了表征.PCSi-1G-C6与M-C6同为相列相,树状物相态由介晶基元相态决定.PCSi-1G-C6的熔点比M-C6低50℃,清亮点比M-C6低16℃,液晶态温区比M-C6宽34℃.     

Liquid crystalline epoxy resin modified cyanate ester/epoxy resin systems

Liquid crystalline epoxy resin (LCE) modify cyanate ester/epoxy resin blend systems were studied by scanning electron microscope, polarizing optical microscope, thermogravimetric analyzer, differential scanning calorimetry, thermal mechanical analysis, and rheometers. With the addition of LCE resin, the blends showed both an enhanced curing rate and increased glass transition temperature of cured samples. The phase structures of the blends changed from homogenous to liquid crystalline phase when the content of LCE was increased. At the same time, the mechanical properties were also improved and thermal expansion coefficients were lowed down. The thermal degradation temperatures showed little differences, while the residue char yields were slightly increased with the addition of LCE. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermotropic liquid crystalline polyesters with terphenyl moieties and flexible ‘ether’ spacers in the main chain

Polyesters with the general formula:

(n=1 (TO 5), 3 (TO 11), 9 (TO 29)) were characterized by differential scanning calorimetry, optical microscopy, miscibility tests and X-ray investigations. In polyesters TO 5 and TO 11 a smectic phase type C occurs. X-ray studies of oriented samples have suggested that the smectic C configuration is azimuthally disordered with the layers orientationally ordered. By contrast, above its melting point the polyester TO 29 shows distinct phases of liquid crystal and isotropic liquid. This is probably due to the polydispersity of the low molecular weight fraction of PEO used in preparing this polyester. A structural model is proposed to illustrate how the polyesters under investigation can adopt organizations compatible with all data known so far.     

Atomic force microscopy (AFM) studies of liquid crystalline polymer (LCP) surfaces

An atomic force microscope (AFM) operating in tapping or contact mode was used to study the surface topography and the molecular organization of Vectra‐A and Vectra‐B films. Large‐scale (15 × 15 μm) AFM images revealed that ribbonlike fibrils with a width/height ≫ 1.0 are the dominant surface features of these liquid crystalline polymers (LCPs). The region of local disorder, surface debris, and interfibrillar debris as well as possible amorphous regions were observed in both LCP samples. Large fibrils, 5.0–10.0 μm in width, can be thought of as formed by smaller microfibrils capable of forming ordered structures. Microfibrils can bend upward, forming raised surface features; bend inward, originating cracks 1–2 μm wide on the film surface; or divide and subdivide into smaller units. Longitudinal and lateral stresses are believed responsible for the variation in fibril size, shape, and orientation. AFM images containing molecular‐scale details showed that microfibrils consists of chains of molecules coiled around a central axis and that they can be only about 2.0 nm wide. These submicron surfaces consist of white spots (representing molecules) that can form ordered structures or that can cluster to form agglomerates distributed in a random manner. Submicron fibrils are believed to represent the LCP basic structural unit. AFM results indicate that the surface topography of Vecta‐B is more ordered and uniform than is the one observed for Vectra‐A. Seemingly, amorphous particles form debris on Vectra‐A surfaces. Short rods oriented crosswise on the fibril surface are instead what increases the Vectra‐B roughness. These LCPs can have a surface topography similar to the one observed in AFM images of a spiderweb. However, the spiderweb fibrils are formed by more uniform microfibrils that are oriented parallel to each other. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2243–2254, 1999     

Synthesis and characterization of cholesteric thermotropic liquid crystalline polyesters

Cholesteric liquid crystalline polyesters were successfully synthesized from isosorbide, methyl hydroquinone, and isophthaloyl chloride. Homo/copolyesters were synthesized by the solution polycondensation method, for which a mild organic base such as pyridine was employed. Inherent viscosities of polyesters P‐3–P‐5 were in the range of 0.31–0.39 dL/g at 25°C in chloroform, and polyesters P‐1 and P‐2 were insoluble in chloroform. Homo/copolyesters based on isosorbide, methyl hydroquinone, and isophthalic acid had thermal stability at more than 300°C on the basis of 10% weight loss. The thermotropic liquid crystalline properties were examined by differential scanning calorimetry and polarizing optical microscopy. Wide‐angle X‐ray diffraction study demonstrated that polyesters P‐1, P‐2, and P‐3 were semicrystalline, whereas the degree of crystallinity of polyesters P‐4 and P‐5 was less than 5%. Copolyester P‐4 showed formation of a yellow iridescent streak at 209°C on heating and development of a Grandjean texture at 270°C on heating. These are typical textures of the cholesteric liquid crystalline phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1232–1237, 2007     

Silicone‐based cholesteric liquid crystalline polymers: Effect of crosslinking agent on phase transition behavior

Silicone‐based cholesteric liquid crystalline polymers (ChLCP) were fabricated with variable clearing temperatures as controlled by their chemical compositions. The chemical structures of the mesogenic monomers and ChLCP were confirmed by FTIR and ¹H‐NMR spectroscopy. The mesogenic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The experimental results demonstrated that the glass transition temperatures and the clearing points of the liquid crystalline polymers decreased with increasing proportion of mesogenic crosslinking agent up to 12.50 mol % (LCP‐3), and at higher proportion of crosslinking agent, the clearing points disappeared, indicating that the network chains have less chance to orient themselves. Thermogravimetric analysis showed that the LCP‐3 was the most stable up to 230°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

侧链聚硅氧烷液晶弹性体的合成与性能研究

综述了国内侧链聚硅氧烷液晶弹性体的研究情况,并对不同类型的侧链聚硅氧烷液晶弹性体的分子结构、结构与性能之间的关系进行了总结。     

A study of the static and dynamic properties of side-chain liquid crystalline polymers in low molar mass mesogens

The static and dynamic properties of solutions of a side chain polysiloxane liquid crystal polymer have been studied in a cyanobiphenyl nematic host as a function of concentration and temperature. Refractive index measurements were carried out on aligned samples and the data used to determine the macroscopic order parameter, S, using Haller's method. Photon correlation spectroscopy has been used to measure ($\text{k}{}_{22}\text{γ}{}_1$) for the pure nematic solvent and the solutions. From these measurements it appears that the static properties vary slowly and linearly with increasing polymer concentration whilst the dynamic or viscoelastic properties change markedly. This change has been attributed to γ₁, the twist viscosity, and the results have been discussed in terms of the function of the siloxane polymer backbone.     

Synthesis and properties of side‐chain liquid‐crystalline polysiloxanes containing hemiphasmidic mesogens

The synthesis of hemiphasmidic monomers 4‐[(3,4,5‐triethoxy)benzoyloxy]‐4′‐[(p‐allyloxy)benzoyloxy]biphenyl (M₁), 4‐[(3,5‐diethoxy)benzoyloxy]‐4′‐[(p‐allyloxy)‐benzoyloxy]biphenyl (M₂), and of the corresponding side‐chain liquid‐crystalline polysiloxanes (P₁, P₂) was carried out. For comparison, rodlike monomer 4‐[(p‐ethoxy)‐benzoyloxy]‐4′‐[(p‐allyloxy)benzoyloxy]biphenyl (M₃) and its polysiloxanes (P₃) were also prepared. The chemical structures of the monomers and polymers obtained were confirmed by FTIR and ¹H‐NMR spectra. Their mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The relationship between structures and properties was discussed. It was observed that M₁ and M₃ were enantiotropic nematic phase, M₂ was monotropic mesophase, and their poly(methylsiloxanes) (P₁–P₃) possessed a broad range enantiotropic nematic phases and high thermal stability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 946–952, 2005     

Synthesis and characterization of thermotropic liquid crystalline poly(aryl ether ketone) copolymers with pendant 3‐(trifluoromethyl) phenyl groups

Novel poly(aryl ether ketone) copolymers with pendant 3‐(trifluoromethyl)phenyl groups were synthesized by the reaction of a crystal‐disrupting monomer, 3‐(trifluoromethyl)phenylhydroquinone (FH) and a mesogenic monomer, 4,4′‐biphenol (BP) with 1,4‐bis(p‐fluorobenzoyl)benzene (BF). Thermotropic liquid crystalline behavior of the copolymers was investigated by means of differential scanning calorimetry, polarized optical microscope and wide‐angle X‐ray diffraction. As a result, the copolymers with the respective molar ratios of FH/BP/BF of 0/100/100–10/90/100 and 80/20/100–100/0/100 were semi‐crystalline without liquid crystalline properties, and amorphous polymers, respectively. In contrast, copolymers with the molar ratio of FH/BP/BF of 20/80/100–70/30/100 had liquid crystalline characteristics. Interestingly, the formation of a highly ordered smectic phase was confirmed for copolymers with the molar ratio of FH/BP/BF of 20/80/100–50/50/100, respectively. All the liquid crystalline copolymers had a wide liquid crystalline temperature range (57–75 °C). Copyright © 2006 Society of Chemical Industry     

Side-chain functionalized liquid crystalline polymers and blends, 10: phase behavior and structure of side-chain liquid crystalline ionomers containing ions of d-metals

Novel side-chain liquid crystalline (LC) ionomers containing d-metals Co(II) and Ni(II) were synthesized and characterized. Both families of the ionomers are characterized by the same influence of charged group content in polymer on their phase behavior. The incorporation of 2-3 mol% of metal ions in the nematic polymer matrix leads to the induction of SmA phase and rise in the clearing point. The peculiarity of their phase behavior in comparison with the earlier investigated LC ionomers with alkaline or alkali-earth metals is the full destruction of the mesophase at the concentration of d-metal higher than 12 mol%. This phenomenon was associated with the well-known ability of the transition metal ions to form various complexes that, in the case of LC ionomers, can negatively influence the ordering of the side mesogenic groups. The proposed structure of the LC ionomers is discussed in comparison with the metallomesogenic polymer systems.     

Synthesis and cure of liquid crystalline diallyl modifiers for bismaleimide resin

Three kinds of liquid crystalline aromatic azomethine modifiers were synthesized with high yield, and the modification of bismaleimide resin (BMI) with them was studied by scanning electron microscope, polarizing optical microscope, thermogravimetric analyzer, differential scanning calorimetry, and rheolometry. Blends cured at the temperature of liquid crystalline phase were found to have oriented liquid crystal‐rich phase and improved mechanical properties. The addition of o,o′‐diallyl bisphenol A in the blends of BMI decreases thermal properties but shows little effect on phase structures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4366–4371, 2006     

Curing behavior of liquid crystalline epoxy/DGEBA blend

The effect of liquid crystalline epoxy (LCE) resin on the curing behavior and thermomechanical properties of diglycidylether of bisphenol A (DGEBA) was investigated. LCE was blended with DGEBA and curing behavior of the blend was studied according to LCE content in the blend. Curing of DGEBA was accelerated and thermomechanical properties of DGEBA were considerably improved by the addition of LCE, which acted as a molecular reinforcement. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007