胆甾液晶弹性体的合成及液晶性能研究

以胆甾液晶单体和向列液晶交联剂与含氢聚硅氧烷接枝聚合制备了一系列弹性体.通过红外光谱(FT-IR)、核磁氢谱(1 H-NMR)确定了液晶单体及弹性体的化学结构.通过差热扫描量热仪(DSC)、偏光显微镜(POM)以及X-射线衍射研究了其介晶性质及液晶相行为.结果表明,弹性体的玻璃化转变温度随着向列液晶交联剂的加入先降低后升高.随着向列液晶交联剂的加入,系列弹性体的X-射线衍射峰弥散,且最大反射波长略微变长,说明液晶分子间的有序性受到干扰.     

Synthesis and properties of liquid crystalline polyurethane elastomers

Novel type of mesogenic chain extenders used in this study are N,N′‐bis(4‐hydroxyphenyl)‐3,4,3′,4′‐biphenyldicarboxyimide (BPDI) and N,N′‐bis[4‐(6‐hydroxyhexyloxy) phenyl]‐3,4,3′,4′‐biphenyldicarboxyimide (BHDI). BHDI has a flexible spacer of 6‐methylene units but BPDI does not. The liquid crystalline polyurethane elastomers were synthesized from BPDI or BHDI as a mesogenic chain extender, 4,4′‐diphenylmethane diisocyanate, and poly(oxytetramethylene)glycol (MW 1000) as a soft segment. Polyurethane based on BHDI exhibited two melting transitions. However, any melting behavior was not shown in the BPDI‐based polyurethanes because of higher melting temperature than decomposition temperature. The composition of polyurethanes was varied as a means of manipulating liquid crystalline behavior and physical properties. The BHDI‐based polyurethanes containing above 50 wt % of hard segment content exhibited nematic liquid crystal behaviors. As the hard segment content of the BHDI‐based polyurethanes increased, the glass transition temperature (T_g), strength, modulus, and the amount of hydrogen bonding increased. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 577–585, 2000     

Body-temperature shape-shifting liquid crystal elastomers

Nematic monodomain liquid crystal elastomers (LCEs) undergo efficient temperature-induced reversible shape-shifting around the nematic-isotropic transition temperature (T_ni) due to the presence of the liquid-crystalline order of mesogens. Usually, the T_ni of nematic LCEs is much higher than the human body temperature, and therefore LCEs are not often considered for biomedical applications. This study describes an LCE system where the T_ni is tuned by substitution of the rigid mesogens RM257 with a flexible backbone PEGDA250. By systematically substituting the RM257 with PEGDA250, the T_ni of LCEs was observed to decrease from 66°C to 23°C. A rate-optimized LCE material was fabricated with 10 mol % rigid mesogens substituted with a flexible backbone that demonstrated T_ni at 32°C, in-between the room temperature of 20°C and the body temperature of 37°C. The T_ni allowed the programmed shape at room temperature, quick shape-shifting upon exposure to body temperature, and before-programmed shape when kept at body temperature. This LCE material displayed reversible length change of 23%, opacity change, and shape change between room temperature and body temperature.     

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 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 of spirocyclosiloxanes for transparent copolymer thermosets

The use of multiple‐ring cyclic molecules to generate crosslinked polymeric materials takes the advantages of small molecular precursors directly, but is retarded by the need of exact reactivity matching between different components. This problem was overcome by use of spirocyclosiloxanes, which were synthesized through the Piers–Rubinsztjan reaction. The two‐level ring strain energies in these spirocyclosiloxanes help them accommodate a wide range of single‐ring cyclic molecules to form highly transparent thermosets. The rich library of spirocyclosiloxanes, single‐ring cyclic molecules, and catalysts makes this modular approach a promising method for the preparation of useful materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46370.     

侧链聚硅氧烷液晶弹性体的合成与性能研究

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

Effect of molecular parameters on thermomechanical behavior of side-on nematic liquid crystal elastomers

We investigated the structure–property relationship of liquid crystal elastomers (LCEs) obtained from a series of nematic side-on monomers. A new synthetic strategy was developed to obtain the acrylate monomers (n-ADBB), which gave us the opportunity to easily modify the spacer lengths of the monomers. Through magnetic field alignment, well-defined LCE micropillars were fabricated from the monomers by a method combining soft lithography and photopolymerization/photocrosslinking of the monomers and a crosslinker. The influence of structural parameters on the thermomechanical deformation of the microstructures was studied through microscopic observations. The study quantitatively revealed the correlation of thermomechanical behavior of the microstructured LCEs with the crosslinking density and length of the flexible spacer linking the mesogenic core to the backbone. With a proper control of the structural parameters, optimized performances such as large reversible contraction, good elasticity and mechanical robustness were demonstrated for this type of LCEs.     

手性液晶材料的研究进展

介绍了手性液晶的发展过程,阐述了手性液晶的结构、分类与应用研究的现状,着重讨论了手性液晶在显示用液晶材料中的重要作用及应用,并对手性液晶的发展前景做了展望。     

Synthesis,characterization, and properties of thermosets based on the cocuring of an acetylene‐terminated liquid‐crystal and silicon‐containing arylacetylene oligomer

A thermotropic acetylene‐terminated liquid‐crystal monomer, 2‐methyl‐1,4‐phenylene bis(4‐ethynylbenzoate) (MPBE), was prepared and used as a modification composition to react and cocure with a silicon‐containing arylacetylene (PSA) oligomer for improving PSA resin. The curing behavior of the PSA–MPBE resins were characterized by differential scanning calorimetry and Fourier transform infrared spectroscopy. The microstructure and morphology of the PSA–MPBE resins were investigated by scanning electron microscopy (SEM) and transmission electron microscopy. Their dynamic mechanical properties and thermostability were measured by dynamic mechanical analysis (DMA) and thermogravimetric analysis. The results indicate that the thermotropic acetylene‐terminated liquid‐crystal monomer melted into a schlieren texture. MPBE and PSA could copolymerize to fix the mesogenic domain in the crosslinked network and form a homogeneous‐phase sea‐island structure, which improved the rigidity and toughness of the materials. DMA showed that the storage modulus of the PSA–MPBE resins increased by about 400 MPa compared to the those of the pure components. The SEM experiments showed a noticeable change in the morphology, from a typical brittle fracture for the pure PSA to microplastic deformation behavior for the PSA–MPBE resins. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45141.     

Synthesis and characterization of four-armed star mesogen-jacketed liquid crystal polymer

The synthesis of four-armed star mesogen-jacketed liquid crystal polymer was achieved by atom transfer radical polymerization in chlorobenzene solution using pentaerythritol terakis(2-bromoisobutyrate) (PT-Br) as an initiator and CuBr/sparteine complex as a catalyst. The results show that the number average molecular weigh is creased linearly vs. monomer conversion, and that the polydispersities were quite narrow (<1.19), which is the character of controlled polymerization. The structure was experimentally confirmed by ¹H NMR. The liquid-crystalline behavior of the four-armed star polymer was studied using DSC and POM. Only the polymer with a M_n,GPC beyond 3.68×10⁴ g/mol formed a liquid crystalline phase which was quite stable with a high clearing point.     

Synthesis and phase behavior of nematic liquid‐crystalline elastomers derived from smectic crosslinking agent

A mesogenic crosslinking agent M‐1 was synthesized to minimize the perturbations of nonmesogenic crosslinking agent for liquid‐crystalline elastomers. The synthesis of side‐chain liquid‐crystalline elastomers containing a rigid mesogenic crosslinking agent M‐1 and a nematic monomer M‐2 was described by a one‐step hydrosilylation reaction. The chemical structures of the obtained monomers and network polymers were confirmed by Fourier transform infrared and ¹H‐NMR 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 was discussed. The liquid‐crystalline elastomers containing less than 15 mol % of the crosslinking units showed elasticity, reversible phase transition, and threaded texture. The experimental results demonstrated that isotropic temperature and liquid‐crystalline range of polymers P‐1–P‐7 decreased a little as the concentration of crosslinking agent M‐1 increased, and the use of mesomorphic crosslinking agent M‐1 promotes the arrangement of liquid‐crystalline units from P‐1 to P‐5. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1712–1719, 2005     

Aromatic bisphenol A-based elastomers via hydrosilylation chemistry

The preparation of highly aromatic elastomers from a bisphenol A-based divinyl-terminated resin and polymerization with various aromatic silane containing compounds utilizing a room temperature hydrosilylation reaction is demonstrated. The polymers exhibit high thermal and oxidative stability with 5% weight losses around 430 and 350°C and char yields ranging from 35% to 40%. The thermosets maintained their elastomeric properties with good hardness and mechanical properties as measured by elongation measurements. The toughness of the thermosets was not improved with the inclusion of aromatic moieties but the hardness did appear to increase with the addition of more aromatic groups.     

Biphenyl liquid crystal epoxy containing flexible chain: Synthesis and thermal properties

A biphenyl type liquid crystal epoxy (LCE) monomer 4,4′-di(2,3-epoxyhexyloxy)biphenyl (LCBP4) containing flexible chain was synthesized and the curing behavior was investigated using 4,4′-diaminodiphenylmethane (DDM) as the curing agent. The effect of curing condition on the formation of the liquid crystalline phase was examined. The cured samples show good mechanical properties and thermal stabilities. Moreover, the relationship between thermal conductivity and structure of liquid crystalline domain was also discussed. The samples show high thermal conductivity up to 0.28–0.31 W/(m*K), which is 1.5 times as high as that of conventional epoxy systems. In addition, thermal conductive filler, Al₂O₃, was introduced into LCBP4/DDM to obtain higher thermal conductive composites. When the content of Al₂O₃ was 80 wt%, the thermal conductivity of the composite reached to 1.86 W/(m*K), while that of diglycidyl ether of bisphenol A (Bis-A) epoxy resin/DDM/Al₂O₃ was 1.15 W/(m*K). Compared with Bis-A epoxy resin, the formation of liquid crystal domains in the cured LCE resin enhanced the thermal conductivity synergistically with the presence of Al₂O₃. Furthermore, the introduction of Al₂O₃ also slightly increased the thermal stabilities of the cured LCE.     

N-苄基壳聚糖液晶材料的制备及表征

以甘氨酸和质量分数36%盐酸为原料合成出甘氨酸盐酸盐离子液体,利用间歇碱处理方式对壳聚糖原料进行处理,制备出脱乙酰度可达92.2%的高脱乙酰度壳聚糖.采用N-烷基化化学改性方法,使苯甲醛与高脱乙酰度壳聚糖分别在乙酸和甘氨酸盐酸盐离子液体两种溶剂中进行反应,制备N-苄基壳聚糖.红外光谱测试表明:由这两种方法制备出的产物均...     

Synthesis and characterization of novel citric acid-based polyester elastomers

In this paper we report successful simple synthesis of unique elastic polyesters by carrying out catalyst-free polyesterification of multifunctional non-toxic monomers: 1,8-octanediol (OD), citric acid (CA) and sebacic acid (SA). The chemical, physical, and surface chemical properties of the resulting copolyester polyoctanediol citrate/sebacate [p(OCS)] have been investigated. This new material was characterized by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF-MS), nuclear magnetic resonance spectroscopy (NMR), thermal analysis (TA), mechanical tests, photo-acoustic Fourier-transform infrared spectroscopy (PA-FTIR), X-ray photoelectron spectroscopy (XPS) and swelling experiments. We demonstrate that the chemical structure, morphology, physical integrity and surface chemistry of the synthesized co-polymer can be controlled by simply varying the initial acid concentration (CA/SA) in the pre-polymer. This novel p(OCS) polymer exhibits versatility in mechanical properties, hydration and hydrolytic degradation as determined by the chemical structure of the polyester elastomer.     

Crack‐healing behavior of epoxy–amine thermosets

This work offers detailed experimental evidence for crack healing in fully formed epoxy–amine polymer networks. Compact tension specimens of diglycidyl ether of bisphenol A (EPON‐828) and 4,4′‐methylene biscyclohexanamine were synthesized at stoichiometry and with an excess or paucity of an amine curing agent. Healing efficiencies were measured on the basis of the regain in the fracture load after a healing protocol was applied. For all systems investigated, the average healing efficiency for first fracture was greater than 50% when healing was conducted at 185°C for 1 h. The crack‐healing behavior was highly repeatable at all stoichiometries, and healing was found to occur for repeated fracture–heal cycles of the same specimen. On the basis of results from size exclusion chromatography for the extractable phase, infrared spectroscopy, and scanning electron microscopy, it is postulated that healing is primarily due to mechanical interlocking of the nodular topology of a fractured crack interface that occurs in the rubbery state and is set in place by vitrification upon cooling. A ½ power dependence of the healing efficiency on the healing time was observed, and this suggests that the interlocking of topographical features is governed by diffusive processes. For networks cured with a large excess of epoxide groups, the recovered fracture load was higher than that of virgin specimens. In this case, polyetherification or homopolymerization of previously unreacted epoxy groups increased the healing efficiency significantly, and this suggests that low degrees of covalent bonding can significantly enhance healing behavior in these systems. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of side-chain liquid crystalline polysiloxanes

The synthesis and characterization are described for a series of side-chain liquid crystal polysiloxanes using polyhydrosilylation reaction between a poly(hydrogen methyl-co-dimethylsiloxanes),-(OSiHMe)_x,-(OSiMe2)_y-, where x/y was 13/87, 30/70, 55/45, 73/27 and 98/2, and [4-(allyloxy)benzoyll biphenyl mesogenic group. The side-chain liquid crystal polysiloxanes were characterized by¹H NMR,¹³C NMR, IR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and optical polarizing microscopy. The dimethylsiloxane segment factors governing thermal transition temperatures and activation energy (E_a) of the nematic-to-isotropic phase transition are discussed.     

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     

Fracture toughness of highly ordered liquid crystalline epoxy thermosets achieved by optimized composition of curing agents

Liquid crystalline (LC) epoxy resin was prepared by using different compositions of aromatic amine as curing agents, in order to control curing rates and chemical compositions. The progress of the curing reaction was investigated based on the gel fraction and epoxy groups of conversion determined by Fourier-transform infrared spectroscopy. The ordered networked polymer structure was analyzed by polarized optical microscopy and X-ray diffraction. Highly oriented network chains in the obtained epoxy thermosets were promoted by the incorporation of flexible chains in the network and the provision of sufficient time for vitrification. Furthermore, it was clarified that a curing temperature higher than T_g is required to promote the transition to the smectic LC phase in order to prepare highly ordered epoxy thermosets. The increase in the formed smectic LC phase in the network chains resulted in significant higher fracture toughness and achieved up to 2.7 times higher value.