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     

Novel thermotropic liquid crystalline polyphosphonates

Main chain liquid crystalline polyphosphonates containing semi-flexible phenylester mesogen with even number of methylene spacers (2-10) have been synthesized. The monomers and polymers were characterized by IR, ¹H, ¹³C and ³¹P NMR spectroscopy. The spectral details are in accordance with the structures. All the polymers were exhibited liquid crystalline property in the Hot stage optical polarized microscope (HOPM). DSC thermal analysis confirms the mesophase formation for all the polymers. The grain size of the liquid crystalline mesophase is increasing with increasing methylene chain. T_g, T_m and T_i of the polymers decreased with increase in spacer length. The T_g of these phosphorus-containing polymers is much lower than that of non-phosphorus polymers containing triad ester mesogens. Energy minimized structures for the molecules which mimic the polymer chain suggests that the reduction in T_g may be due to entanglement raised by incorporation of phosphorus heterogeneity.     

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     

Side‐chain liquid‐crystalline polymers with a limonene‐co‐methyl methacrylate main chain: Synthesis and characterization of polymers with phenyl benzoate mesogenic groups

A new series of liquid‐crystalline polymers with a polymer backbone of limonene‐co‐methyl methacrylate were synthesized and characterized, and the spacer length was taken to be nine methylene units. The chemical structures of the obtained olefinic compound and polymers were confirmed with elemental analysis and proton nuclear magnetic resonance spectroscopy. The thermal behavior and liquid crystallinity of the polymers were characterized with differential scanning calorimetry and polarized optical microscopy. The polymers exhibited thermotropic liquid‐crystalline behavior and displayed a glass‐transition temperature at 48°C. The appearance of the characteristic schlieren texture confirmed the presence of a nematic phase, which was observed under polarized optical microscopy. These liquid‐crystalline polymers exhibited optical activity. A comparison was also made with polyacrylates and polymethacrylate‐based materials. This revealed that the nature of the polymer backbone had a major effect on the liquid‐crystalline properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4595–4600, 2006     

Investigation of liquid crystalline and photocrosslinkable poly[4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamate]s

Three series of liquid‐crystalline‐cum‐photocrosslinkable polymers were synthesized from 4‐x‐phenyl‐4′‐(m‐methacryloyloxyalkyloxy)cinnamates (x = ? H, ? OCH₃ and ? CN; m = 6, 8 and 10) by free radical solution polymerization using azobisisobutyronitrile as an initiator in tetrahydrofuran at 60 °C. All the monomers and polymers were characterized using intrinsic viscosity, and FTIR, ¹H NMR and ¹³C NMR spectroscopy. The liquid crystalline behavior of these polymers was examined using a hot stage optical polarizing microscope. All the polymers exhibited liquid crystalline behavior. The hexamethylene spacer‐containing polymers exhibited grainy textures; in contrast, the octamethylene and decamethylene spacer‐containing polymers showed nematic textures. Differential scanning calorimetry data confirmed the liquid crystalline property of the polymers. Thermogravimetric analysis revealed that all the polymers were stable between 236 and 344 °C in nitrogen atmosphere and underwent degradation thereafter. As the methylene chain length increases in the polymer side‐chain, the thermal stability and char yield of the polymers decrease. The photocrosslinking property of the polymers was investigated using the technique of exposing the polymer solution to UV light and using UV spectroscopy. The crosslinking reaction proceeds via 2π–2π cycloaddition reactions of the ? CH?CH? of the pendant cinnamate ester. The polymers containing electron‐releasing substituents (? OCH₃) showed faster crosslinking than the unsubstituted polymers and those containing electron‐withdrawing substituents (? CN). Copyright © 2007 Society of Chemical Industry     

Synthesis and characterization of side‐chain liquid‐crystalline polyacrylates containing azobenzene moieties

Syntheses of novel liquid‐crystalline polymers containing azobenzene moieties were performed by a convenient route with an acrylate backbone. The azobenzenes were key intermediates of the monomers, and side‐chain liquid‐crystalline polymers were prepared, that is, poly[α‐{4‐[(4‐acetylphenyl)azo]phenoxy}alkyloxy]acrylates, for which the spacer length was 3 or 11 methylene units. In addition, poly[3‐{4‐[(3,5‐dimethylphenyl)azo]phenoxy}propyloxy]acrylate was prepared with a spacer length of 3 methylene units. The structures of the precursors, monomers, and polymers were characterized with Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR techniques. The polymers were obtained by conventional free‐radical polymerization with 2,2′‐azobisisobutyronitrile as an initiator. The phase‐transition temperatures of the polymers were studied with differential scanning calorimetry, and the phase structures were evaluated with a polarizing optical microscopy technique. The results showed that two of the monomers and their corresponding polymers exhibited nematic liquid‐crystalline behavior, and one of the monomers and its corresponding polymer showed smectic liquid‐crystalline behavior. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2653–2661, 2002     

Liquid crystalline and photocrosslinkable poly(4,4′‐stilbeneoxy) alkylarylphosphates

Three series of liquid crystalline and photocrosslinkable poly(4,4′‐stilbeneoxy) alkylarylphosphates were synthesized from various 4,4′‐bis(m‐hydroxyalkyloxy)stilbenes (m = 2, 4, 6, 8, 10) and arylphosphorodichloridates in chloroform by solution polycondensation method. Polarized optical microscope (POM) and differential scanning calorimetry (DSC) observations revealed that polymers containing less than four methylene spacer groups did not exhibit liquid crystalline (LC) texture, possibly due to smaller microdomain and restricted movement of the mesogen. In contrast, polymers containing more than four methylene spacer group established LC texture, which has been attributed to the larger monodomain and free movement of mesogens. Thermogravimetric analysis (TGA) data indicated that thermal stability and char yield decreased with increasing flexible methylene spacer groups, increased significantly for biphenyloxy and 1‐naphthyloxy containing polymers than that of phenyloxy containing polymers ascribed to increasing aromaticity, size, and number of aromatic rings. Photocrosslinking of stilbene containing polymers has been shown to proceed via 2π‐2π cycloaddition reaction by Ultra‐violet (UV) and fluorescence. The rate photocrosslinking has been found to increase with increasing number of methylene group in the main chain. The aromaticity of the side chain also increases the rate of crosslinking. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Synthesis and thermal properties of polythioether‐based liquid‐crystalline polymers containing azobenzene in the side chain

BACKGROUND: Owing to the unusual structural rearrangement of polychloromethylthiirane (PCMT) at room temperature, it has not been used as the main‐chain backbone of side‐chain liquid‐crystalline polymers (SLCPs). However, it has been observed that PCMT has a relatively stable and clear structure under special conditions. Therefore, we attempted to synthesize SLCPs using PCMT as main‐chain backbone and investigated their thermal behavior. RESULTS: New polymers, poly[1‐({(4‐methoxyazobenzene‐4′‐oxy)alkyl}thio)‐2,3‐epithiopropane], in which the number of methylene units in the alkyl group is 4, 5 or 6, were prepared by means of reactions of corresponding (4‐methoxyazobenzene‐4′‐oxy)alkylthiols with PCMT. The structures of these compounds were confirmed using elemental analysis and ¹H NMR spectroscopy. The substitution ratios of the copolymers with 4, 5 and 6 methylene units in the alkyl group were 56, 75 and 80%, respectively. Differential scanning calorimetry measurements and polarized optical microscopy observations showed that the resulting copolymers exhibited thermotropic liquid‐crystalline mesomorphism with nematic phase except for the copolymer with a 56% substitution ratio. The decomposition temperature of all the synthesized copolymers was near 195 °C. CONCLUSION: This investigation has demonstrated that PCMT polymerized for 8 h has the ability to act as a suitable main‐chain backbone for SLCPs. Moreover, SLCPs could be obtained only by the reaction of PCMT with thiolate salt containing mesogenic groups. The substitution ratios increased with increasing number of methylene groups in the spacer. Copyright © 2009 Society of Chemical Industry     

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 liquid crystalline ionomers with polymethylhydrosiloxane main-chain- and side-chain-containing sulfonic acid groups

A novel thermotropic side-chain liquid crystalline ionomer (LCI) containing sulfonic acid groups on the side-chain was synthesized by graft copolymerization of mesogenic monomer 4-allyloxy-benzoxy-4′-methoxyphenyl (ABM) and nonemesogenic monomer 4-allyloxy-azobenzene sulfonic acid (AABS) upon polymethylhydrosiloxane (PMHS). The chemical structures of the polymers were confirmed by IR spectroscopy. DSC and TGA were used to measure the thermal properties of those polymers and the mesogenic properties were characterized by polarized optical micrography (POM), DSC, and WAXD. The clearing point temperature (T_c) of these liquid crystalline ionomers was enhanced 50–60°C compared with the polymer without ionic groups. The LCIs exhibit a broad smectic mesogenic region of 80–90°C; the thermal stability below 200°C of the polymers decreases with increasing sulfonic acid concentration. The inherent viscosity of 0.5% solutions decreased with increasing sulfonic acid concentration in the polymer chains. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1555–1561, 1998     

Poly(alkyl lactate acrylate)s having tunable hydrophilicity

Four alkyl lactates and alkyl lactate acrylates having methyl, ethyl, propyl, and butyl as alkyl moiety were synthesized by azeotropic distillation. Their formation was confirmed by Fourier transform infrared (FTIR), mass, ¹H nuclear magnetic resonance (NMR) and proton decoupled ¹³C NMR spectroscopic techniques. Solution polymerization was carried out for these alkyl lactate acrylates and the formed homopolymers were characterized by FTIR, ¹H NMR, proton decoupled ¹³C NMR spectroscopic, and gel permeation chromatographic techniques. Shear thinning behavior was observed for all the polymers. Wide angle X‐ray Diffraction studies showed that the polymers were amorphous in nature and also exhibited odd‐even effect among alkyl lactate groups with respect to average molecular interchain spacing. Depending on the length of the alkyl lactate groups, relative humidity and time, the hydrophilicity of the polymers decreased with increase in the length of the alkyl lactate group among the odd and even series. Among the studied polymers, poly(ethyl lactate acrylate) may have the potential for hydrogel applications, due to its highly hydrophilic nature. T_g decreased with increase in length of alkyl lactate groups. Trend observed on the thermal stabilities of poly(alkyl lactate acrylate)s could be explained on the basis of average molecular interchain spacing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40962.     

Synthesis and properties of TLCPs with 2,6‐naphthalene‐based mesogen,polymethylene spacer,and nonlinear 4,4′‐thiodiphenyl links

A series of new thermotropic main‐chain liquid crystalline copolyesters were prepared by polycondensation of 2,6‐naphthalenedicarbonyl chloride, 4,4′‐thiodiphenol, and α,ω‐alkanediols (n = 4–10) in diphenyl ether at 200°C. Thermal transition behaviors of these copolyesters were investigated by differential scanning calorimetry. Moreover, their thermal stabilities and mesomorphic textures were studied by thermogravimetric analysis and polarizing optical microscopy, respectively. Corresponding model compounds with terminal mesogenic units and central polymethylene spacers were also synthesized for comparison. Both copolymers and model compounds exhibit odd–even dependency of melting temperatures, transition enthalpy (ΔH_m), and entropy (ΔS_m) on the number of methylene units in the spacer. However, the odd–even effects in model compounds are much more distinctive. Nematic mesophases are the only texture observed in melts, except the model compounds with longer methylene units (n = 8, 10), in which smectic mesophases can be observed. The T_m values of the copolyesters (TDP/HD = 1/1) are between 233 and 259°C, depending on spacer length. The initial decomposition temperatures of the copolyesters are above 419°C under N₂ atmosphere. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1536–1546, 2002     

Influence of chirality on phase behaviour of side chain liquid crystalline polymers

Summary Two kinds of chiral side chain liquid crystalline polyacrylates were synthesized and characterized by DSC, POM and x-ray diffraction. The results indicated that chirality of side chain end group and spacer length strongly influence the phase behaviour of the polymers. The polymer P-I with one asymmetric carbon atom of end group exhibits enantitropic Smectic S_A and S_C phases. The polymer P-III having two asymmetric carbon atoms displays enantitropic Smectic S_A and S_B phases. Formation of liquid crystalline polymorphism of polymers depends on spacer length of side chains.     

Synthesis and characterization of side‐chain liquid‐crystalline ionomers containing quaternary ammonium salt groups

A series of thermotropic side‐chain liquid‐crystalline ionomers (LCIs) containing 4‐(4‐alkoxybenzyloxy)‐4′‐allyloxybiphenyl (M) as mesogenic units and allyl triethylammonium bromide (ATAB) as nonmesogenic units were synthesized by graft copolymerization upon polymethylhydrosiloxane. The chemical structures of the polymers were confirmed by IR spectroscopy. DSC was used to measure the thermal properties of these polymers. The mesogenic properties were characterized by polarizing optical microscopy, DSC, and X‐ray diffraction. Homopolymers without ionic groups exhibit smectic and nematic mesophases. The nematic mesophases of the ionomers disappear and the mesomorphic temperature ranges decrease with increasing concentration of ionic units. The influence of the alkoxy chain length on clearing temperature (T_c) values of ionomers clearly shows an odd‐even effect, similar to that of other side‐chain liquid‐crystalline polymers. The mesomorphic temperature ranges increase with increasing alkoxy chain length when the number of alkoxy carbon is over 3. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2879–2886, 2003     

Mesomorphic properties of cholesteric side‐chain liquid crystalline polysiloxanes and elastomers

A series of crosslinked liquid crystalline polymers and corresponding uncrosslinked liquid crystalline polymers were prepared by graft copolymerization. Their liquid crystalline properties were characterized by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The results showed that the crosslinking obtained in the isotropic state and the introduction of nonmesogenic crosslinking units into a polymeric structure could cause additional reduction of the clearing point (T_i) of the crosslinked polymers, compared with the corresponding uncrosslinked polymers. The crosslinked polymers (P‐2–P‐4) with a low crosslinking density exhibited cholesteric phases as did the uncrosslinked polymers. In contrast, a high crosslinking density made the crosslinked polymer P‐5 lose its thermotropic liquid crystalline property. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 773–778, 2004     

Synthesis and X-ray diffraction of ferroelectric liquid crystalline polysiloxanes containing 4′-(2-chloro-3-methylpentanoyloxy)-4-alkanyloxybiphenyl side groups

Summary The synthesis and characterization of side-chain liquid crystalline polysiloxanes containing (2S,3S)-4-(2-chloro-3-methylpentanoyloxy)-4-alkanyloxybiphenyl side groups are presented. All the obtained polymers exhibit smectic mesomorphism. Those polymers containing a spacer length longer than 8 methylene units reveal respectively enantiotropic S_A, S _* ^C and S_B phases. The result demonstrates that the tendency toward the S _* ^C phase increases with increasing the spacer length.     

Synthesis, characterization and liquid crystalline behavior of poly(monomethyl itaconate)s with new pendant cholesterol moieties

In order to investigate the effects of cholesteryl pendant groups on inducing liquid crystalline (LC) phase formation, a new series of cholesteryl-modified poly(monomethyl itaconate) (PMMI-Chol-C₆) have been synthesized from poly(monomethyl itaconate) (PMMI) and 6-(cholesteryloxycarbonyloxy) hexanol (Chol-C₆) with different degrees of substitution (DS_chol). All the obtained compounds were characterized by conventional spectroscopic methods. The DS_chol values of the modified PMMI were obtained by ¹H NMR spectroscopy and conductometric titration. The inherent viscosities of polymers were determined by an Ubbelohde viscometer at 35 °C in DMSO solution. The resulting products of modified PMMA polymers were soluble in a variety of organic solvents, and the solubility improved by increasing the DS_chol. Thermal behavior and optical properties of Chol-C₆ and PMMI-Chol-C₆ polymers were investigated by thermal gravimetric analysis, differential scanning calorimetry and hot-stage polarizing optical microscopy. The glass transitions of the modified PMMI polymers occurred at lower temperatures than the parent PMMI. It was found that among the synthesized polymers with different molar ratios of the substitution, only the PMMI-Chol-C₆ (1) polymer bearing 77 mol% of the side chains, with reduced melting point and increased thermal stability, formed thermotropic liquid crystalline smectic phases. This polymer exhibited wider mesophase than the mesogenic side chain Chol-C₆ and amorphous morphology. The results of a comparative study on the structure and properties of the polymers showed that liquid crystalline polymers may be achieved through the attachment of mesogenic cholesterol side chain onto the main chain via methylene chains of side branches.     

The Effect of the Structural Elements on the Properties of Side Chain Mesomorphic Polymers

The thermal properties of mesomorphic polymers depend on the relative amounts of the different structural elements (hard core, flexible chains, main chain) of the polymer. Literature data are compared with the conclusions obtained from the three-component thermodynamic model of side chain mesomorphic polymers. The effects of the different soft elements (main chain, spacer and p-alkyl or alkoxy chain) depend first of all on the length of the spacer and its interaction with the main chain. The thermal properties of the polymer can be well regulated by varying the different structural elements of the homo- and co-polymers. The glass transition temperature (T_g) of the polymer can be reduced by building O and N atoms into the main chain and/or by binding the side chains on 3rd, 4th, etc. atoms of the main chain. The T_g can be further reduced by increasing the length of the spacer. If the spacers are long enough, the layer type structures are favored, with p-alkoxy chains behaving also as a plasticizer of the main chain. The clearing point can be influenced by copolymerization of monomers with different hard cores. The three-component thermodynamic model of side-chain mesomorphic polymers well explains the effect of different structural elements on the structure and properties of these polymers.     

Synthesis and thermotropic liquid‐crystalline behavior of novel main‐chain poly(aryl ether ketones)

Novel aromatic poly(ether ketones) containing bulky lateral groups were synthesized via nucleophilic substitution reactions of 4,4′‐biphenol and (4‐chloro‐3‐trifluoromethyl)phenylhydroquinone (CF‐PH) with 1,4‐bis(p‐fluorobenzoyl)benzene. The copolymers were characterized by differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction, and polarized light microscopy observation. Thermotropic liquid‐crystalline behavior was observed in the copolymers containing 40, 50, 60, and 70 mol % CF‐PH. The crystalline–liquid‐crystalline transition [melting temperature (T_m)] and the liquid‐crystalline–isotropic phase transition appeared in the DSC thermograms, whereas the biphenol‐based homopolymer had only a melting transition. The novel poly(aryl ether ketones) had glass‐transition temperatures that ranged from 143 to 151°C and lower T_m's that ranged from 279 to 291°C, due to the copolymerization. The polymers showed high thermal stability, and some exhibited a large range in mesophase stability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1347–1350, 2003     

Synthesis and characterization of highly functionalized polymers based on N,N,N′,N′-tetraalkyl-4,4′-diaminostilbene and maleic anhydride

Novel, highly functionalized rod-like copolymers have been synthesized by alternating copolymerization of N,N,N′,N′-tetraalkyl-4,4′-diaminostilbenes (TDASs) with maleic anhydride. These unique copolymers have been characterized by SEC, DSC and TGA. The solubility of these copolymers in organic solvents is strongly dependent on the length of the alkyl chains on the amino groups and the solubility in aqueous media is pH dependent. Light scattering studies indicate that the conformation of the polymer backbone does not change upon increasing temperature or introducing charges to the amino groups. High chain rigidity is further corroborated by the high T_g of the polymers. There is no observed glass transition below 280 °C. The light scattering and thermal results are indicative of a rod-like backbone structure.