Synthesis and phase behavior of side‐chain liquid‐crystalline polymers containing malachite green lactone groups

New side‐chain liquid‐crystalline polymers containing both cholesteric and thermochromic side groups were synthesized. Their chemical structures were confirmed with elemental analyses and Fourier transform infrared, proton nuclear magnetic resonance, and carbon‐13 nuclear magnetic resonance spectra. The mesogenic properties and phase behavior were investigated with differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction measurements. The effect of the concentration of dye side groups on the phase behavior of the polymers was examined. The polymers showed smectic or cholesteric phases. Those polymers containing less than 20 mol % dye groups had good solubility, reversible phase transitions, wider mesophase temperature ranges, and higher thermal stability. The experimental results demonstrated that the isotropization temperature and mesophase temperature ranges decreased with an increasing concentration of dye groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3870–3878, 2004     

Preparation and phase behavior of side‐chain cholesteric liquid‐crystalline elastomers

A series of new side‐chain cholesteric elastomers derived from cholesteryl 4‐(10‐undecylen‐1‐yloxy)‐4′‐ethoxybenzoate and phenyl 4,4′‐bis(10‐undecylen‐1‐yloxybenzoyloxy‐p‐ethoxybenzoate) was synthesized. The chemical structures of the monomers were confirmed by elemental analyses, Fourier transform infrared, and ¹H NMR and ¹³C NMR spectra. The mesomorphic properties of elastomers were investigated with differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction measurements. The influence of the content of the crosslinking unit on the phase behavior of the elastomers was examined. Monomer M₁ showed a cholesteric phase, and M₂ displayed smectic and nematic phases. The elastomers containing <15 mol % of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3315–3323, 2005     

Side-chain cholesteric liquid crystalline elastomers derived from a mesogenic crosslinking agent: I. Synthesis and mesomorphic properties

The synthesis of new side-chain cholesteric elastomers derived from a cholesteric monomer and mesogenic crosslinking agent is presented. The chemical structures of the monomers obtained were confirmed by elemental analyses, FT-IR, ¹H NMR, and ¹³C NMR. The mesomorphic properties and thermal stability were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), polarizing optical microscopy (POM), and X-ray diffraction (XRD) measurements. M₁ showed cholesteric phase, and M₂ displayed enantiotropic nematic phase and monotropic smectic phase. The elastomers containing less than 12 mol% of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability.     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4'-allyloxybiphenyl 4'-ethoxybenzoate, M₁), a chiral crosslinking agent (isosorbide 4-allyloxybenzoyl bisate, M₂) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂. The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X-ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂-P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145-209.6°C, with no changed on the cooling. Polymers P₄-P₇, with more than 6 mol % of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15 mol % of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

Synthesis and properties of cholesteric liquid crystalline elastomers

The synthesis of new side-chain cholesteric liquid crystalline elastomers, containing the flexible non-mesogenic crosslinking agent M-1 and the cholesteric monomer M-2, is described by a one-step hydrosilication reaction. The chemical structures of the monomers and network polymers obtained were confirmed by FT-IR spectroscopy. Their mesogenic 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 network polymers showed elasticity, reversible phase transitions, and cholesteric Grandjean texture. The experimental results demonstrated that the glass transition temperatures and isotropization temperatures of network elastomers decreased as the concentration of crosslinking units was increased, but the cholesteric phase was not disturbed.     

Mesomorphic properties of side-chain cholesteric liquid-crystalline elastomers

New monomer cholesteryl 4-(10-undecylen-1-yloxybenzoyloxy)-4′-ethoxybenzoate (M₁), crosslinking agent biphenyl 4,4′-bis(10-undecylen-1-yloxybenzoyloxy-p-ethoxybenzoate) (M₂) and a series of side-chain cholesteric elastomers were prepared. The chemical structures of the monomers and elastomers obtained were confirmed by element analyses, FT-IR, and ¹H NMR. The mesomorphic properties and thermal stability were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction measurements. The influence of the content of the crosslinking unit on the phase behavior of the elastomers was examined. M ₁ showed cholesteric phase, and M ₂ displayed nematic phase. The elastomers containing less than 12 mol% of the crosslinking units revealed reversible mesomorphic phase transition, wide mesophase temperature ranges, and high thermal stability.     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4′‐allyloxybiphenyl 4′‐ethoxybenzoate, M₁ ), a chiral crosslinking agent (isosorbide 4‐allyloxybenzoyl bisate, M₂ ) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂ . The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X‐ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂ –P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145–209.6°C, with no changed on the cooling. Polymers P₄ –P₇ , with more than 6?mol?% of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15?mol?% of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

Side-chain cholesteric liquid crystalline elastomers containing isosorbide as chiral agent – synthesis and characterisation

In this work the new-style nematic monomer M₁ , chiral crosslinking reagent M_C and a series of new side-chain cholesteric liquid crystalline elastomers derived from M₁ and M_C were prepared. The effect of the content of the chiral crosslinking unit on phase behaviour of the elastomers has been discussed. Polymer P₁ showed nematic phase, P₂ –P₇ showed cholesteric phase, P₃ formed Grandjean texture in the heating cycle and turned out a blue Grandjean texture in the cooling cycle, P₂ –P₃ with less than 6 mol% of chiral crosslinking agent gave rise to selective reflection. The elastomers containing less than 15 mol% of the crosslinking units displayed elasticity, reversible phase transition and high thermal stability. Experimental results demonstrated that the glass transition temperatures reduced first and then increased, and the isotropisation temperatures and the mesophase temperature ranges decreased with increasing content of crosslinking unit.     

Synthesis and characterization of liquid crystalline elastomers bearing fluorinated mesogenic units and crosslinking mesogens

Several new side‐chain liquid crystalline (LC) polysiloxanes and elastomers ( IP ‐ VIP ) bearing fluorinated mesogenic units and crosslinking mesogens were synthesized by a one‐step hydrosilylation reaction with poly(methylhydrogeno)siloxane, a fluorine‐containing LC monomer 4′‐undec‐10‐enoyloxy‐biphenyl‐4‐yl 4‐fluoro‐benzoate and a crosslinking LC monomer 4′‐(4‐allyloxy‐benzoxy)‐biphenyl‐4‐yl 4‐allyloxy‐benzoate. The chemical structures and LC properties of the monomers and polymers were characterized by use of various experimental techniques such as FTIR, ¹H‐NMR, EA, TGA, DSC, POM and XRD. The effect of crosslinking mesogens on mesomorphic properties of the fluorinated LC polymers was studied as well. The obtained polymers and elastomers were soluble in many solvents such as toluene, tetrahydrofuran, chloroform, and so forth. The temperatures at which 5% weight loss occurred (T_d) were greater than 250°C for all the polymers, and the weight of residue near 600°C increased slightly with increase of the crosslinking mesogens in the fluorinated polymer systems. The samples IP , IIP , IIIP and IVP showed both smectic A and nematic phases when they were heated and cooled, but VP and VIP exhibited only a nematic mesophase. The glass transition temperature (T_g) of polymers increased slightly with increase of crosslinking mesogens in the polymer systems, but the mesophase–isotropic phase transition temperature (T_i) and smectic A–nematic mesophase transition temperature (T_S‐N) decreased slightly. It suggests that the temperature range of the mesophase became narrow with the increase of crosslinking mesogens for all the fluorinated polymers and elastomers. In XRD curves, the intensity of sharp reflections at low angle decreased with increase of crosslinking mesogens in the fluorinated polymers systems, indicating that the smectic order derived from fluorinated mesogenic units should be destroyed by introduction of more crosslinking mesogens. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis and characterization of side-chain cholesteric elastomers derived from an isosorbide crosslinking agent

New liquid crystalline monomer 4-(4-ethoxybenzoyloxy)biphenyl-4′-[(10-undecylen-1-yloxy)-4′-ethoxy]benzoate (M ₁ ), chiral crosslinking agent isosorbide di-(10-undecylen-1-yloxybenzoate) (M ₂ ), and the corresponding elastomers were prepared. The chemical structures of M ₁ and M ₂ were characterized by Fourier transform infrared and ¹H-nuclear magnetic resonance. The mesomorphic properties and phase behavior were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X-ray diffraction measurements. M ₁ exhibited typical threaded texture and droplet texture of nematic phase. The use of chiral crosslinking agent in the polymer networks could induce cholesteric phase. The elastomers containing less than 10 mol% of the chiral crosslinking units showed elasticity, reversible phase transition, wide mesophase temperature ranges, and high thermal stability. For the elastomers P ₂ –P ₄ , the glass transition temperature (T _g) increased; clearing temperature (T _i) and mesophase temperature range (ΔT) decreased with increasing content of the crosslinking unit.     

Preparation and properties of siloxane liquid crystalline elastomers with a mesogenic crosslinking agent

A mesogenic crosslinking agent M-1 was synthesized to minimize the perturbations of non-mesogenic crosslinking agents in liquid crystalline elastomers. The synthesis of new side chain liquid crystalline elastomers containing the rigid mesogenic crosslinking agent M-1 and nematic monomer M-2 by a one-step hydrosilylation reaction is described. The chemical structures of the monomers and network polymers obtained were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties and phase behaviour were investigated by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction. The influence of the crosslinking units on phase behaviour is discussed. Liquid crystalline elastomers containing less than 15 mol % of the crosslinking units showed elasticity, reversible phase transitions and a threaded texture. The experimental results demonstrated that the glass transition temperature of polymers P-1-7 increased with increasing concentration of crosslinking agent M-1; but the isotropic temperature and liquid crystalline range decreased slightly.     

Synthesis and characterization of a series of side chain chiral smectic liquid crystalline elastomers

A series of new chiral smectic liquid crystalline elastomers was prepared by graft polymerization of a nematic monomer with a chiral and non‐mesogenic crosslinking agent, using polymethylhydrosiloxane as backbone. The chemical structures of the monomers and polymers obtained were confirmed by FTIR and ¹H NMR. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X‐ray diffraction. Monomer M ₁ showed a nematic phase during heating and cooling. Polymer P ₀ exhibited a smectic B phase; elastomers P ₁–P ₃ showed the smectic A phase, P ₄–P ₆ showed a chiral smectic C(SmC*), and P ₇ displayed stress‐induced birefringence. Elastomers containing less than 15?mol?% M ₂ displayed elasticity, reversible phase transitions with wide mesophase temperature ranges, and high thermal stability. With increasing content of the crosslinking unit, glass transition temperatures first increased, then fell, then increased again; isotropization temperatures and mesophase temperature ranges steadily decreased.     

Crosslinking of vinyl‐terminated biphenyl and naphthalene side‐chain liquid‐crystalline poly(epichlorohydrin) derivatives

We performed the crosslinking of vinyl‐terminated biphenyl and naphthalene side‐chain liquid‐crystalline polyethers using peroxide‐type initiators with and without the addition of tertiary amine promoters. The crosslinking temperatures were chosen in the range of mesophase stability to allow the mesophase order to be frozen. The biphenyl derivatives, with a high isotropization temperature, were crosslinked to a large extent. This led to anisotropic thermosets. To crosslink naphthalene derivatives, amine promoters were needed, but degrees of crosslinking were lower, and anisotropic elastomers were obtained. Crosslinking processes were studied by differential scanning calorimetry, polarized optical microscopy, and Fourier transform infrared spectroscopy. The nature of the frozen mesophase was confirmed by X‐ray diffraction studies on mechanically oriented samples. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2237–2244, 2002     

Synthesis and crosslinking of biphenyl and naphthalene liquid‐crystalline polyethers with pendant full‐saturated and vinyl‐terminated aliphatic chains

Two series of vinyl‐terminated, side‐chain liquid‐crystalline polyethers containing 4,4′‐biphenyl and 2,6‐naphthalene moieties as mesogenic cores with several contents of vinyl crosslinkable groups were synthesized by chemically modifying poly(epichlorohydrin) with mixtures of saturated and vinyl‐terminated mesogenic acids. In most cases the degree of modification was over 90%. The polymers were characterized by chlorine analysis, IR and ¹H and ¹³C NMR spectroscopies, viscometry, size exclusion chromatography/multi‐angle laser light scattering, and thermogravimetric analysis. The liquid‐crystal behavior of all the synthesized polymers was examined by differential scanning calorimetry, polarized optical microscopy (POM), and X‐ray diffraction on mechanically oriented samples. The crosslinking of most polymers was done by peroxide‐type initiators, which generally led to liquid‐crystal elastomers. The mesophase organization was maintained on the crosslinked materials, as confirmed by POM and X‐ray diffraction. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3384–3399, 2003     

Side chain cholesteric liquid crystalline elastomers: synthesis and phase behaviour

A series of new side chain cholesteric liquid crystalline elastomers (P-2-P-6) containing the nematic crosslinking monomer 4-(10-undecen-1-yloyloxy)benzoyl-4'-allyloxybenzoyl-p-benzenediol bisate (M-1) and the cholesteric monomer 4-cholesteryl 4-(10-undecen-1-yloyloxy)benzoate (M-2) were synthesized. The chemical structures of the monomers and elastomers obtained were confirmed by FTIR and ¹H NMR spectroscopy. Their liquid crystalline properties and phase behaviour were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. The effect of the crosslinking units on phase behaviour is discussed. Elastomers containing less than 20 mol % of the crosslinking units showed elasticity, reversible phase transitions and cholesteric Grandjean texture. The experimental results demonstrated that the glass transition and isotropization temperatures of P-2-P-6 increased with the increasing concentration of crosslinking unit M-1.     

含胆固醇和 4-(反式-正烷基环己基)苯甲酸结构单元的双液晶基元液晶化合物的合成及其性质

本文合成了一系列含有胆固醇和4-（反式-正烷基环己基）苯甲酸结构单元的新型双液晶基元液晶化合物。这些化合物中两个介晶基元是利用不同长度的氧烷酰基连接在一起。利用FT-IR、MS、1H NMR、POM、DSC 表证了所得化合物的结构和介晶性,并选择几种双液晶基元液晶测定了它们的机械黏度和在主体液晶中的螺旋扭曲力（HTP)。结果表明,绝大多数化合物显示较低相变温度的胆甾相（N*）,并且被选择的化合物的平均机械黏度和螺旋扭曲力类似于或优于胆甾醇任酸酯。     

Synthesis and properties of polysiloxane side chain cholesteric elastomers

The synthesis of new side chain cholesteric liquid crystalline elastomers containing the flexible non-mesomorphic crosslinking agent M-1 and the cholesteric monomer M-2 by a one-step hydrosilylation reaction is described. The chemical structures of the obtained monomers and network polymers 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. The glass transition temperatures and isotropic temperatures of the mesomorphic elastomers decreased as the concentration of crosslinking units increased; in the mesomorphic region the liquid crystalline elastomers showed elasticity, reversible phase transitions and Grandjean texture. The flexible crosslinking agent did not disturb the cholesteric structure; moreover, it was beneficial for adjusting the helix of the cholesteric liquid crystalline polymers, and cholesteric elastomers P-6, P-7, show reversible selective reflection of visible light.     

Vinyl‐terminated liquid‐crystalline dendrimers based on dendritic polyols and their siloxane‐based elastomers

A new series of side‐chain liquid‐crystalline dendrimers (LCDs) by grafting vinyl‐terminated phenyl benzoate‐based promesogens to a novel polypropyleneimine‐derived dendritic polyols are reported. Polarized optical microscopy and X‐ray diffraction studies show that both the compounds display a smectic‐A (SmA) mesophase. The second‐generation dendrimer bearing eight‐branched promesogens exhibits a more stable SmA mesophase with a wide mesomorphic temperature range. It is demonstrated that “promoting groups” in the structure of LCD for the enhancement of mesomorphic stability are unnecessary in the case of strong anisotropic interactions. In contrast to conventional LCDs, these two compounds possess reactive vinyl terminals that endow them with the potential for the preparation of polymeric materials. For the first time, a type of thermoset elastomers is explored from LCDs via hydrosilylation crosslinking reaction of vinyl terminals and siloxane crosslinker. Two‐dimensional X‐ray diffraction study indicates that the lamellar structures of original dendrimers are reserved in the elastomer networks. Stress–strain curves reveal that these elastomers exhibit excellent elasticity under successive uniaxial compression. The combination of anisotropic structures of rigid units and elasticity of flexible networks in this novel series of elastomers makes them promising candidates for the application in artificial muscles or cartilages. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Synthesis and characterization of a series of side chain chiral smectic liquid crystalline elastomers

A series of new chiral smectic liquid crystalline elastomers was prepared by graft polymerization of a nematic monomer with a chiral and non-mesogenic crosslinking agent, using polymethylhydrosiloxane as backbone. The chemical structures of the monomers and polymers obtained were confirmed by FTIR and ¹H NMR. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X-ray diffraction. Monomer M₁ showed a nematic phase during heating and cooling. Polymer P₀ exhibited a smectic B phase; elastomers P₁-P₃ showed the smectic A phase, P₄-P₆ showed a chiral smectic C(SmC*), and P₇ displayed stress-induced birefringence. Elastomers containing less than 15 mol % M₂ displayed elasticity, reversible phase transitions with wide mesophase temperature ranges, and high thermal stability. With increasing content of the crosslinking unit, glass transition temperatures first increased, then fell, then increased again; isotropization temperatures and mesophase temperature ranges steadily decreased.     

侧链胆甾液晶聚合物及弹性体的液晶性能研究

把胆甾液晶单体 4 烯丙氧基苯甲酸胆甾醇酯 (Mch)分别和向列液晶单体 4 烯丙氧基苯甲酰氧基 4′ 甲氧基苯 (Mn) ,向列液晶交联剂 2 叔丁基对苯二酚双 [4 (6 丙烯酰氧基己氧基 )苯甲酸酯 ](Mnc)接枝到聚硅氧烷链上 ,得到系列侧链液晶聚合物Pn 系列和液晶弹性体Pe 系列 .通过热分析、偏光显微分析和X 射线分析等手段分别研究了向列液晶单体和向列液晶交联剂对含同一胆甾液晶基元聚合物的影响 .结果表明 ,向列液晶单体的摩尔百分比在 80 %以下 ,液晶聚合物Pn 系列为胆甾型液晶 ,在研究的范围内 ,液晶弹性体Pe 系列也为胆甾型液晶 ,Pn 系列和Pe 系列都具有较宽的液晶相范围 ,热分解温度均在 2 80℃以上 .