Synthesis,characterization, and thermotropic properties of side-chain liquid crystalline polysiloxane polymers with an oligo(ethylene oxide) unit in the side chain

A series of new alkene and octenyloxy monomers containing 4′-[oligo(ethylene oxide)] n monomethyl ether 4-biphenyl ether carboxyl benzoate [MS3BDBE_n] (n = to 3) and 1- (p-methoxydiphenyl)–(carboxyl benzoate) [oligo(ethylene oxide)]n [MS_m+2BEnDB] (m = 1, 6; n = 1 to 3) as end groups were synthesized. The molecular structure of the monomers was charaterized using nuclear magnetic resonance (NMR) spectroscopy. These monomers were grafted onto poly(methylhydrosiloxane)s (PMHS) by the platinun-catalyzed hydrosilylation process. The thermal transition temeratures and mesophase textures of the monomers and the polysiloxane polymers have been determined by diffential scanning calorimetry (DSC) and by polarized optical microscopy. The effect of changes in chemical structure on the mesophase properties, glass transition temperature, isotropic temperature, and mesophase texture of the monomers and the polysiloxane polymers is discussed. Polymers PS3BDBEn showed smectic and nematic phases which were not analogous to their precursor nematic monomers MS3BDBEn. Both monomers MS_m+2BE_nDB and their polymeric homologous PS_m+2BE_nDB did not exhibit mesophase properties. This demonstrated that the polymer effect could not stabilize the mesophase obtained from mesogenic core which contained a flexible oligo(ethylene oxide) unit interconnecting aromatic group. © 1995 John Wiley & Sons, Inc.     

An X-ray investigation of terminally carboxyl oligo (ethylene oxide) monomethyl ethers-substituted side-chain liquid crystalline polysiloxanes

4′-[Oligo(ethylene oxide) monomethyl ether carbonyl] biphenyl-4-yl 4-(alkenyloxy) benzoate side-chain liquid crystalline (LC) polysiloxane polymers with various lengths of a terminal group and spacer were prepared. The mesophase structure and transition temperature of those polymers were investigated using methods of X-ray diffraction, polarized optical microscopy, and differential scanning calorimetry, respectively. The mesophases of the polymers were smectic ones. The layer spacing d1s and the side-chain distance of d2s obtained were around 29–34 Å and 4.4–4.6 Å, respectively. d1s were much shorter than twice the lengths of the side chains presumed in the fully extended conformation. Hence, the two-layer end-on packings or the packing with overlapping of tails model seemed not able to interpret the mesophase structure of those polymers studied. The effects of temperature on the mesophase microstructure of 4′-[ethylene oxide monomethyl ether carbonyl] biphenyl-4-yl 4-(pentenyloxy) benzoate side-chain LC polysiloxane polymer were also studied using the X-ray diffraction method. It was found that both d1 and d2 of the polymer in the mesophase temperature range became shorter with decreasing temperature and the long-and short-range order could remain, to some extent, at temperatures above the isotropic transition temperature and temperatures below the melting temperature. © 1993 John Wiley & Sons, Inc.     

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 high molecular weight side chain liquid crystalline/photoactive polymers

Various liquid crystalline and photoactive azobenzene monomers were synthesized and attached to copoly(methyl methacrylate‐glycidyl methacrylate) [copoly (MMA‐GMA)] to get high molecular weight side chain liquid crystalline (LC)/photoactive copolymers. Further, spacers are generated in situ and reactive groups are obtained after the modification. All monomers and polymers were thoroughly characterized by FTIR, ¹H and ¹³C NMR, UV‐VIS spectrophotometry, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, and polarized optical microscopy. All side chain LC polymers showed higher thermal stability than that of copoly(MMA‐GMA). Three LC and one azo monomer exhibited characteristic nematic mesophase where as one LC monomer has shown nematic and sanded smectic‐A texture. The rate of trans‐cis isomerization of polymer was lower than that of the monomer and both monomers and polymers showed slow back isomerization. Present approach offers convenient way to synthesize high/desired molecular weight photoactive LC polymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New thermochromic liquid–crystalline polymer: Synthesis and phase behavior

A series of new thermochromic side‐chain liquid–crystalline polymers were prepared. The chemical structures of the resulting monomers and polymers were characterized by element analyses, FTIR, ¹H‐NMR, and ¹³C‐NMR. Their mesogenic properties were investigated by differential scanning calorimetry, thermogravimetric analyses, polarizing optical microscopy, and X‐ray diffraction measurements. The influence of the content of dye groups on phase behavior of the polymers was discussed. The polymers P₁–P₃ showed smectic phase, and P₄–P₇ revealed cholesteric phase. The polymers containing less than 30 mol % of the dye groups showed good solubility, reversible phase transition, wider mesophase temperature ranges, and higher thermal stability. Experimental results demonstrated that the clearing temperature and mesophase temperature ranges decreased with increasing the concentration of the dye groups. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 329–335, 2005     

Time resolved WAXS study of the role of mesophase in oriented crystallisation of poly(ethylene terephthalate-co-isophthalate) copolymers

Poly(ethylene terephthalate-co-isophthalate) copolymers containing up to 18 mol% isophalate have been drawn at 90 °C at a deformation rate of ∼15 s⁻¹ while recording two dimensional wide angle X-ray scattering patterns. All polymers, including homopolymer controls, show the development of an oriented smectic mesophase during the last stages of deformation. After the end of deformation, the mesophase decays and is replaced by oriented triclinic crystals which increase according to first order transformation kinetics. The characteristic meridional spacing of the smectic mesophase reduces systematically with increasing isophthalate comonomer and indicates that the comonomer participates in the smectic structure. Unlike isotropic crystallisation from the melt, the crystallinity and crystallisation rate show little variation with comonomer content. This is attributed to the fact that both monomers participate in the intermediate smectic mesophase.     

Synthesis and phase behavior of chiral side‐chain liquid‐crystalline polysiloxanes containing two mesogenic groups

The synthesis of chiral side‐chain liquid‐crystalline polysiloxanes containing both cholesteryl undecylenate (M_I) and 4‐allyloxy‐benzoyl‐4‐(S‐2‐ethylhexanoyl) p‐benzenediol bisate (M_II) mesogenic side groups was examined. The chemical structures of the obtained monomers and polymers were confirmed with Fourier transform infrared spectroscopy or ¹H‐NMR techniques. The mesomorphic properties and phase behavior of the synthesized monomers and polymers were investigated with polarizing optical microscopy, differential scanning calorimetry, and thermogravimetric analysis (TGA). Copolymers IIP–IVP revealed a smectic‐A phase, and VP and VIP revealed a smectic‐A phase and a cholesteric phase. The experimental results demonstrated that the glass‐transition temperature, the clearing‐point temperature, and the mesomorphic temperature range of IIP–VIP increased with an increase in the concentration of mesogenic M_I units. TGA showed that the temperatures at which 5% mass losses occurred were greater than 300°C for all the polymers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2670–2676, 2002     

Synthesis,characterization, and mesomorphic behavior of side-chain liquid crystalline copolysiloxane polymers I. with an oligo (ethylene oxide) unit and a cyano unit in the side chain

The syntheses and characterizations of poly [4-allyloxy-benzoic acid [4-(2-methoxy) ethoxy] biphenyl]-4-yl ester-co-4-allyloxy-[(4-cyano)-4-phenyl] carboxyl benzoate ester (poly [(MS3BDBE1)-co-(MCN)]_x/y) (where x/y represents the molar ratio of the two structural units on the side chain) were performed in this study. The molar compositions of the structural units on the copolymers side chain were characterized by¹H NMR. The transition temperatures, mesophase texture, and layer spacing (dl) of the polysiloxane polymers and copolymers were determined by differential scanning calorimetry (DSC), polarized optical microscopy, and X-ray diffraction patterns. The effects of the molar composition in the copolymers on the mesophase texture, transition temperatures, enthalpy/entropy change of mesophase/isotropic transition, dl of these copolymers were also discussed.     

Effect of the different rigidity of the chiral crosslinker on phase behaviors of side‐chain chiral liquid crystalline elastomers

In the present work, the phase behaviors of two series of side‐chain liquid crystalline elastomers ( PI and PII series) derived from the same nematic liquid crystalline monomer and the different rigidity of chiral bisolefinic crosslinking units have been compared and studied extensively, and the effect of the different rigidity of crosslinker on the phase behavior of elastomers has been discussed. The chemical structure of the monomers and polymers obtained were confirmed by FTIR and ¹H NMR spectroscopy. The phase behaviors were investigated by differential scanning calorimetry, polarizing optical microscopy measurement, thermogravimetric analyses, and X‐ray diffraction measurement. The two series of elastomers showed smectic or cholesteric phases. When the amount of different crosslinking units was less than 15 mol %, both of the elastomers displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. It is shown that the isotropization temperature values of PII series are higher than those of PI series, and the glass transition temperature values of PII series varied smoothly and that of PI series changed smoothly first and then abruptly with increasing the contents of crosslinkers with different rigidity. In addition, PI series showed an interesting change in LC texture near clearing point, but PII series did not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and structure of polysiloxane liquid crystalline elastomers with a mesogenic crosslinking agent

A new mesogenic crosslinking agent M‐1 was synthesized to minimize the perturbations of a nonmesogenic crosslinking agent for liquid crystalline elastomers. The synthesis of new side‐chain liquid crystalline elastomers containing a rigid mesogenic crosslinking agent M‐1 and a nematic monomer M‐2 is described by a one‐step hydrosilylation reaction. The chemical structures of the obtained monomers and elastomers were confirmed by ¹H NMR and FTIR spectroscopy. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. The influence of the crosslinking units on the phase behavior is discussed. The elastomers containing less than 15 mol % of the crosslinking units showed elasticity, reversible phase transition, and nematic‐threaded texture. However, when the crosslinking density reached 21.6 mol %, the mesophase of polymer P‐8 disappears. The adoption of a mesogenic crosslinking agent diminishes the perturbation of a nonmesogenic crosslinking agent on mesophase of liquid crystalline elastomers, and isotropic temperature and a mesomorphic temperature range slightly decreased with increasing content of the crosslinking agent. In addition, X‐ray analysis shows nematic polydomain network polymers can transform into smectic monodomain by stress induction, leading to the orientation formation macroscopically. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1736–1742, 2004     

Synthesis and characterization of a series of smectic liquid crystalline elastomers

A series of new smectic and cholesteric liquid crystalline elastomers was prepared by graft polymerization of mesogenic monomer with the chiral and nonmesogenic crosslinking agent using polymethylhydrosiloxane as backbone. The chemical structures of the monomers and polymers obtained were confirmed by Fourier transform infrared (FTIR), proton nuclear magnetic resonance spectra (¹H‐NMR). The mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and X‐ray diffraction measurements (XRD). M₁ showed smectic (S_B, S_C, S_A) and nematic phases during the heating and the cooling cycles. Polymer P₀ and elastomer P₁ exhibited smectic B phase, elastomers P₂–P₅ showed smectic A phase, P₆ and P₇ showed cholesteric phase, and P₈ displayed stress‐induced birefringence. The elastomers containing less than 15 mol % M₂ displayed elasticity and reversible phase transition with wide mesophase temperature ranges. Experimental results demonstrated that the glass transition temperatures decreased first and then increased; melting temperatures and the isotropization temperatures and the mesophase temperature ranges decreased with increasing content of crosslinking unit. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 498–506, 2005     

Synthesis and characterization of chiral side‐chain liquid‐crystalline polymer containing menthol ester

The synthesis of new chiral side‐chain liquid‐crystalline polysiloxanes containing p‐(allyoxy)benzoxy‐p‐chlorophenyl (ABCH) as mesogenic units and undecylenic acid menthol ester (UM) as chiral nonmesogenic units is presented. The chemical structures of monomers and polymers are confirmed by IR spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) are used to measure thermal properties of those polymers. Mesogenic properties are characterized by polarized optical microscope (POM), DSC, and small‐angle X‐ray diffraction. Analytic results revealed that polymers P₀–P₆ are thermotropic liquid‐crystalline polymers with low glass transition; Polymers P₂–P₆ exhibit chiral smectic liquid‐crystalline properties with marble texture, optical rotation, and a sharp reflection at low angles in X‐ray diffraction; polymers P₀, P₁ only exhibit smectic liquid‐crystalline properties without chirality; and P₇ only exhibits chirality without liquid‐crystalline properties. All the polymers exhibit good thermal stability with temperature of 5% mass loss over 297°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2845–2851, 2003     

Synthesis,structure, and phase behavior of new chiral liquid‐crystalline polysiloxanes based on mesogenic menthyl monomers

Six new chiral monomers ( M ₁ – M ₆ ), and their corresponding side chain polymers ( P ₁ – P ₆ ) containing menthyl groups were synthesized. The chemical structures of M ₁ – M ₆ were characterized with FTIR and ¹H NMR. The structure–property relationships of the monomers and polymers obtained are discussed. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction measurements. Some compounds containing menthyl groups formed mesophase when a flexible spacer was inserted between the mesogenic core and the menthyl groups by reducing the steric hindered effect. The monomers M ₁ , M ₄ , and M ₅ did not reveal mesomorphic properties because of the weaker rigid core or the longer flexible terminal groups, whereas M ₂ , M ₃ , and M ₆ all revealed cholesteric phase. Except P ₄ and P ₅ , the homopolymers P ₁ – P ₃ and P ₆ showed a smectic A phase. In addition, melting, glass transition temperature, or clearing temperature increased, and the mesophase temperature range widened with increasing the rigidity of mesogenic core or decreasing the length of the flexible spacer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Side‐chain copolymers containing smectic monomer and chiral reagent—Synthesis and characterization

A series of new chiral side‐chain liquid‐crystalline polymers were prepared containing smectic‐nematic monomer and nonmesogenic chiral monomer. All polymers were synthesized by graft polymerization using polymethylhydrosiloxane as backbone. The mesomorphic properties were investigated by differential scanning calorimetry, polarizing optical microscopy, thermogravimetric analyses, and X‐ray diffraction measurements. The chemical structures of the monomers and polymers obtained were confirmed by Fourier transform infrared, proton nuclear magnetic resonance spectra (¹H NMR). M₁ showed smectic (S_B, S_C) and nematic phase on the heating and the cooling cycle. Polymers P₀–P₂ were in chiral smectic A phase, while P₃–P₅ were in cholesteric phase, P₆ has bad LC properties, and P₇ has no LC properties. Experimental results demonstrated that nonmesogenic chiral moiety and LC mesogenic with long carbochain offered the possibility of application because of its lower glass transition temperature, and the glass transition temperatures and isotropization temperatures and the ranges of the mesophase temperature reduced with increasing the contents of chiral agent. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Europium‐containing cholesteric liquid crystalline polymers in the side chain

Europium‐containing cholesteric liquid crystalline polymers were graft copolymerized using poly(methylhydrogeno)siloxane, cholesteryl 4‐(allyloxy)benzoate (M₁), cholesteryl acrylate (M₂), and a europium complexes monomer (M₃). The chemical structures of the monomers were characterized by Fourier transform infrared and ¹H‐nuclear magnetic resonance. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermo gravimetric analysis, polarizing optical microscopy, and X‐ray diffraction. With an increase of europium complexes units in the polymers, the glass transition temperature (T_g) did not change significantly; the isotropic temperature (T_i) and mesophase temperature range (ΔT) decreased. All polymers showed typical cholesteric Grandjean textures, which was confirmed by X‐ray diffraction. The temperatures at which 5% weight loss occurred (T_d) were greater than 300°C for the polymers. The introduction of europium complexes units did not change the liquid crystalline state of polymer systems; on the contrary, the polymers were enabled with the significant luminescent properties. With Eu³⁺ ion contents ranging between 0 and 1.5 mol %, luminescent intensity of polymers gradually increased and luminescent lifetimes were longer than 0.45 ms for the polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40866.     

Thermotropic comblike polymers with lipobiphenyl side chains: Factors governing nature of mesophases

In this article we describe the thermotropic behavior of comblike polymers with three types of main chains (polyacrylamide, polymethacrylamide, and polystyrylamide), two lengths of spacers (10 or five methylene groups), and three types of mesogenic cores (biphenyl, carbonitrilbiphenyl, and 2-methyl-1-butoxybiphenyl). The spacers are always linked to the mesogens by an ester bond. All the polymers are smectic at room temperature and exhibit two different smectic phases as a function of temperature, except for the polymer with a styrylamide main chain and a carbonitrilbiphenyl mesogen that presents only one mesophase; but the type of smectic phases is governed by the nature of both the main chain and the substituent R of the biphenyl core. Polyacrylamide polymers exhibit only bilayer smectic phases whose type is determined by the nature of the substituent R of the biphenyl; the smectic phases are SI2 and SC2 for R = H, SC2 and SA2 for R = CN, and SF2 and SC2 for R = O—CH₂—CH(CH₃)—C₂H₆. On the contrary, polymethacrylamide and polystyrylamide polymers exhibit two perpendicular monolayer smectic phases, SB1 and SA1, except for R = CN where a SAd phase replaces the SA1 phase. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2407–2417, 1997     

Synthesis and characterization of side‐chain cholesteric liquid‐crystalline polymers derived from steroid substituents

A series of new cholesteric liquid‐crystalline polysiloxanes derived from steroid substituents were synthesized. The chemical structures of the monomers or polymers obtained were characterized by FTIR, element analyses, ¹H NMR, and ¹³C NMR. Their mesogenic properties and thermal stability were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction measurements. Monomers exhibited typical cholesteric focal‐conic or spiral texture. The polymers P ₁? P ₆ showed cholesteric phase and P ₇ displayed smectic phase. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Synthesis and characterization of side‐chain liquid‐crystalline elastomers containing cholesterol

A series of new smectic and cholesteric liquid‐crystalline elastomers were prepared by graft polymerization of mesogenic monomer with the chiral and nonmesogenic crosslinking agent using polymethylhydrosiloxane as backbone. The chemical structures of the monomers and polymers obtained were confirmed by Fourier transform infrared and proton nuclear magnetic resonance spectra. The mesomorphic properties were investigated by differential scanning calorimetry, polarizing optical microscopy, and X‐ray diffraction measurements. M₁ showed cholesteric phase during the heating and the cooling cycle. Polymer P₁, elastomers P₂ and P₃ exhibited smectic phase, elastomers P₄? P₆ showed chiral smectic C phase, P₇ showed cholesteric phase, and P₈ displayed stress‐induced birefringence. The elastomers containing less than 15 mol % M₂ displayed elasticity and reversible phase transition with wide mesophase temperature ranges. Experimental results demonstrated that the glass transition temperatures, the isotropization temperatures, and the mesophase temperature ranges decreased with increasing content of the crosslinking unit. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 383–390, 2005     

Synthesis and characterization of ferroelectric side chain liquid crystal polymers bearing banana-shaped chiral mesogens

A series of ferroelectric liquid crystal polymers having banana-shaped side chain mesogens were synthesized through photo-polymerization of epoxide moiety. 2,5-disubstituted-thiophene sub-unit was used in synthesizing the banana-shaped monomers. These liquid crystal compounds were characterized by NMR, differential scanning calorimetry (DSC) and optical polarized microscopy (POM). Mesomorphism was investigated as a function of spacer units. All the synthesized low molar mass banana-shaped compounds exhibit smectic blue phase, but chiral smectic C phase could be observed only on compounds having longer spacer. The clearing temperature of low molar mass compounds fluctuated a little when spacer length varies. All polymers exhibit cholesteric mesophase and an observable glass transition. These liquid crystalline compounds reveal strong photoluminescence at visible region (λ_max = 475 nm for M9EPX) and have potential use in polarized organic light emitting diode materials.