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1.
In this work the new-style nematic monomer M1 , chiral crosslinking reagent MC and a series of new side-chain cholesteric liquid crystalline elastomers derived from M1 and MC 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.  相似文献   

2.
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 1P 3 showed the smectic A phase, P 4P 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.  相似文献   

3.
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.  相似文献   

4.
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.  相似文献   

5.
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  相似文献   

6.
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-2P-6 increased with the increasing concentration of crosslinking unit M-1.  相似文献   

7.
The synthesis of two cholesteric monomers (M1 and M2), nematic crosslinking agent (C1 and C2), and the corresponding side-chain elastomers containing menthyl groups (P1 and P2 series) is described. The mesomorphism was investigated by differential scanning calorimetry, polarizing optical microscopy, X-ray diffraction, and thermogravimetric analysis. The effect of the content of the different nematic crosslinking unit on the mesomorphism of the elastomers was discussed. M1 and M2 showed cholesteric and blue phases; C1 and C2 showed nematic phase. Because of the introduction of the nematic crosslinking unit, elastomers P1-1−P1-5 and P2-1−P2-5 exhibited cholesteric phase. With increasing the content of nematic crosslinking unit, T g of the obtained elastomers revealed an increased tendency, and T i of P1 series firstly increased then decreased, while T i of P2 series decreased the mesomorphism of the corresponding elastomers when the content of nematic crosslinking unit was 12 mol.%.  相似文献   

8.
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.  相似文献   

9.
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.  相似文献   

10.
A series of new chiral side-chain liquid crystalline polymers (P1–P7) have been synthesized with poly(methylhydrogeno)siloxane, two chiral liquid crystalline monomers, cholesteryl-4-allyloxybenzoate (M1) and cholesteryl 4-(10-undecylen-1-yloxy) benzoate (M2), and a nematic liquid crystalline monomer, 4-(trifluoromethyl)phenyl 4-(undec-10-enoyloxy)benzoate (M3). The chemical structures and liquid crystalline properties of the synthesized polymers have been investigated by FTIR, 1H-NMR, differential scanning calorimetry (DSC), polarizing optical microscopy (POM), thermogravimetric analysis (TGA), and X-ray diffraction (XRD). All chiral polymers show wide mesophase temperature ranges and a high thermal stability with decomposition temperatures (T d) at 5 % weight loss greater than 300 °C. P1–P4 display a single cholesteric phase, but P5–P7 containing more fluorinated units show a smectic A (SA) phase besides a cholesteric phase. The optical properties of the polymers have been characterized by circular polarization spectra and optical rotation analysis. The cholesteric polymers P3 and P4 exhibit different colors at room temperature, and the color can remain over 24 months. The maximum reflection bands of polymers P1–P4 shift to long wavelength with increasing the content of M3 in the polymer systems. For P5–P7, the reflection wavelengths change sharply around the temperature of the SA–Ch phase transition. The specific rotation value of P2 smoothly decreases from ?8.2° to ?0.29° when it is heated, but the specific rotation value of polymer P7 changes from negative value to positive value on heating cycle. The optical properties of the polymers offer tremendous potential for various optical applications.  相似文献   

11.
The synthesis is described of four new chiral liquid crystalline monomers (M2–M5 ) and their corresponding side‐chain homopolysiloxanes (P2–P5 ) containing menthyl groups. Chemical structures were characterised using FT‐IR or 1H NMR spectra, and specific optical rotations were evaluated with a polarimeter. The phase behaviour and mesomorphic properties of the new compounds were investigated by differential scanning calorimetry, thermogravimetric analysis, polarising optical microscopy, UV/visible/NIR spectrocopy and X‐ray diffraction. The monomers and homopolymers with more aryl segments showed noticeably lower specific optical rotation value. The monomers M2–M5 formed a cholesteric or blue phase when a flexible spacer was inserted between the rigid mesogenic core and the terminal menthyl groups by reducing the steric effect. M2–M5 revealed enantiotropic cholesteric phase. Moreover, M2 also exhibited a monotropic smectic A (SmA) phase, and M4 also exhibited a cubic blue phase on cooling. The selective reflection of light shifted to the long wavelength region with increasing rigidity of the mesogenic core for M2–M5 . P2–P5 exhibited SmA phases, and the mesogenic moieties were ordered in smectic orientation with their centres of gravity in planes. Melting or glass transition temperature and the clearing temperature increased, and the mesophase temperature range widened with increasing rigidity of the mesogenic core.  相似文献   

12.
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 (Td) 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 (Tg) of polymers increased slightly with increase of crosslinking mesogens in the polymer systems, but the mesophase–isotropic phase transition temperature (Ti) and smectic A–nematic mesophase transition temperature (TS‐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.  相似文献   

13.
A series of liquid crystalline polymers (LCPs) have been synthesised by two cholesteric monomers M1, M2 and a nematic monomer M3. The chemical structures and liquid crystalline properties of the monomers and polymers have been characterised by FTIR, 1H-NMR, differential scanning calorimetry, thermogravimetric analyses, X-ray diffraction measurements and polarising optical microscopy. All LCPs show a high thermal stability with wide mesophase temperature ranges. For polymer P1 bearing only cholesteric LC monomers component, it shows a cholesteric phase, whereas others display a blue phase besides a cholesteric phase. The formation of the blue phase is based on the structures of the polymers and the produced biaxial helix. The glass transition temperature and isotropic temperature of the polymers decrease on heating cycle with increasing the content of M3 in the polymers. The specific rotation values of the polymers are temperature-sensitive. The reflection spectra of polymers P1P6 show that the maximum reflected wavelengths shift to long wavelength with increasing the content of M3 in the polymer systems. The frequency and intensity of the bands change sharply at the temperature where cholesteric phase changes to blue phase, but they show a weak dependence on temperature in the blue phase.  相似文献   

14.
Chiral monomer (M1 ), mesogenic and non-mesogenic crosslinking agents (C1 and C2 ), and the corresponding liquid crystalline elastomers (P1 and P2 series), have been synthesised. Their chemical structures have been characterised by Fourier transform infrared or 1H nuclear magnetic resonance and their phase behaviour investigated by differential scanning calorimetry, polarising optical miscoscopy, thermo-gravimetric analysis (TGA) and X-ray diffraction. The effect of the crosslinking unit on the phase behaviour of the elastomers has been studied. M1 showed a cholesteric oily streak and focal conic texture. C2 exhibited a nematic enantiotropic thread-like and schlieren texture, and a monotropic fan-shaped texture in the SA phase. Due to the introduction of the mesogenic crosslinking unit, elastomers, P2-1 ?P2-5 , exhibited a cholesteric phase, while elastomers, P1-1 ?P1-4 , derived from a non-mesogenic crosslinking unit, exhibit a SA phase. As the content of the crosslinking unit increased, the T g of the P1 series initially decreased and then increased, and the T i of the series decreased. In the P2 series the T g increased, but the T i initially increased and then decreased. TGA confirmed that all the elastomers had improved thermal stability.  相似文献   

15.
A series of new cholesteric side-chain liquid crystalline polymers were prepared containing cholesteric 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 and X-ray diffraction measurements, and temperature-changing solidistic optical rotation. The chemical structures of the monomers and polymers obtained were confirmed by Fourier transform infrared and proton nuclear magnetic resonance spectra. M1 showed cholesteric phase during the heating and the cooling cycle. Polymer P1 were chiral smectic A phase, whereas P2–P7 were cholesteric phase. Experimental results demonstrated that nonmesogetic chiral moity offered the possibility of application because of its lower glass-transition temperature, and the glass-transition temperatures and isotropization temperatures reduced, and the ranges of the mesophase temperature changed abruptly at first and then smoothly with increasing the content of chiral agent.  相似文献   

16.
The synthesis of four new chiral mesogenic monomers (M1–M4) and side chain ferroelectric liquid crystalline polymers containing (2S, 3S)-2-chloro-3-methylpentanoate is described. The chemical structures and phase behaviour of the monomers and polymers obtained in this study were characterised by Fourier transform infrared, proton nuclear magnetic resonance, polarising optical microscopy, differential scanning calorimetry, thermogravimetric analysis and X-ray diffraction. The selective reflection of light was investigated with ultraviolet/visible (UV/Vis). Their structure–mesomorphism relationships were discussed. M1 and P1 all showed a chiral smectic C (SmC*) phase. M2 and M3 revealed a SmC* phase and cholesteric phase, while their corresponding polymers P2 and P3 revealed a SmC* phase and smectic A (SmA) phase. M4 only exhibited a cholesteric phase, whereas the corresponding polymers P4 showed a SmA phase. Moreover, the selective reflection of light shifted to the long-wavelength region at the SmC* phase range and to the short-wavelength region at the cholesteric range with increasing temperature, respectively. The results seemed to demonstrate that the tendency towards melting temperature (Tm), glass transition temperature (Tg), isotropic temperature (Ti) and mesophase range for the monomers and polymers increased by increasing the mesogenic core rigidity or the number of phenyl ring. The polymerisation effect could lead to higher liquid crystalline to isotropic phase transition temperature, wider mesophase range and more ordered smectic phase formed. In addition, all the obtained polymers had a very good thermal stability and the corresponding Td increased by increasing the number of phenyl ring.  相似文献   

17.
New side‐chain cholesteric liquid‐crystalline elastomers containing cholesteryl 4‐allyloxybenzoate as cholesteric mesogenic units and biphenyl 4,4′‐bis(10‐undecen‐1‐ylenate) as smectic crosslinking units were synthesized. The chemical structures of the olefinic compounds and polymers obtained were confirmed by element analysis, Fourier transform infrared, proton nuclear magnetic resonance, and carbon‐13 nuclear magnetic resonance spectra. The mesogenic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy, and X‐ray diffraction measurements. The influence of the concentration of the crosslinking unit on the phase behavior of the elastomers was examined. The elastomers containing less than 17 mol % of the crosslinking units revealed elasticity, reversible mesomorphic phase transition, wider mesophase temperature ranges, and higher thermal stability. The experimental results demonstrated that the glass‐transition temperature, isotropization temperature, and mesophase temperature ranges decreased with an increasing concentation of the crosslinking unit. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5262–5270, 2004  相似文献   

18.
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.  相似文献   

19.
To study structure–mesomorphism relationships of the monomers and polymers based on menthol, four new chiral monomers ( M1 – M4 ) and the corresponding homopolymers ( P1 – P4 ) with menthyl group were synthesized. Their chemical structures, formula, phase behavior, and thermal stability were characterized by FTIR, 1H NMR, 13C NMR, elemental analyses, differential scanning calorimetry, polarizing optical microscopy, X‐ray diffraction, and thermogravimetric analysis. The selective reflection of light was investigated with ultraviolet/visible spectrometer. The influence of the mesogenic core rigidity, spacer length, and menthyl steric effect on the mesomorphism of M1 – M4 and P1 – P4 was examined. By inserting a flexible spacer between the mesogenic core and the terminal menthyl groups, four target monomers and polymers could form the expected mesophase. Moreover, their melting temperature (Tm), glass transition temperature (Tg), clearing temperature (Ti), and mesophase range (ΔT) increased with increasing the mesogenic core rigidity; whereas the Tm and Tg decreased, Ti and ΔT increased with an increase of the spacer length. M1 and M2 showed monotropic and enantiotropic cholesteric phase, respectively, whereas M3 and M4 all revealed chiral smectic C (SmC*), cholesteric and cubic blue phases. In addition, with increasing temperature, the selective reflection of light shifted to the long wavelength region at the SmC* phase range and to the short wavelength region at the cholesteric range, respectively. P1 and P2 only showed a smectic A (SmA) phase, whereas P3 and P4 exhibited the SmC* and SmA phases. All the obtained polymers had very good thermal stability. © 2012 Wiley Periodicals, Inc. J. Polym. Sci. Part A: Polym Chem, 2012  相似文献   

20.
A series of chiral fluorinated liquid-crystalline elastomers (LCEs) IP-VIP are prepared by 4-cyano-3-fluorophenyl 4′-(undec-10-enoyloxy)biphenyl-4-carboxylate, isosorbide bis(4-allyloxybenzoate) and 2,4,6,8-tetramethylcyclotetrasiloxane via Pt-catalyzed hydrosilylation. The chiral crosslinking moieties increase from IP to IVP. The elastomers IP, IIP, and IIIP containing low content of chiral crosslinking moieties display SC * liquid-crystalline phase, but IVP, VP, and VIP do not show SC * phase except for N* mesophase. The mesophase is testified according to typical diffractogram measured by X-ray diffraction (XRD) analysis. The layer spacings of the LCEs decrease from IP (d-spacing of 34.2 Å) to VIP (d-spacing of 31.6 Å) with increase of chiral crosslinking groups in the polymers systems. Moreover, the optical properties are performed by ultraviolet–visible–near-infrared spectrophotometry. VP and VIP containing the most chiral crosslinking moieties display maximum reflection in near infrared spectra in the measurement of optical properties, while IP, IIP, IIIP, and IVP do not show obvious maximum reflection. It is interesting that a specific reflection of circularly polarized light appears along with a changing mesophase due to high enough concentration of chiral crosslinking dopants for VP and VIP. All these results suggest that the chiral crosslinking moieties exert influence on the structures of these kinds of LCEs.  相似文献   

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