一种手性薄荷单体对侧链液晶聚合物性能的影响研究

由非液晶手性薄荷单体M1和胆甾醇类液晶单体M2与聚甲基含氢硅氧烷（PMHS）接枝共聚合成了系列新型侧链液晶聚合物。运用红外光谱分析（FTIR）、氢核磁共振谱分析（1H NMR）、差示扫描量热分析（DSC）、热失重（TG）分析、偏光显微分析（POM）、旋光分析（SORT）和X-射线衍射分析（XRD）等进行表征。单体M2在升温和降温过程中呈现胆甾相液晶织构，M2均聚物P1为手性近晶A相，P2～P7为胆甾相液晶。实验结果显示，随着单体M1含量的增加，聚合物的左旋光活性越来越强，玻璃化温度强呈现先降低后升高趋势，清亮点温度Ti降低，液晶相范围变窄。     

含2种介晶基元的液晶弹性体合成与性能研究

合成了一种向列液晶单体（M1）和一种新型手液晶交联单体（M2）,与含氢聚硅氧烷（PM-HS）接枝共聚。交联剂的摩尔分数从0－20%,得到了一系列侧链液晶弹性体P1－P7。通过差式扫描量热仪（DSC）、偏光显微镜（POM）和X-射线分析等手段对聚合物的结构、液晶性能及热性能进行了表征。结果表明,聚合物P1为向列液晶聚合物,P2－P6为胆甾液晶弹性体,P7没有液晶性。随着交联单体M2摩尔分数在体系中的增加,聚合物的玻璃化转变温度（Tg）、清亮点（Ti）和介晶范围逐渐降低。     

胆甾相液晶与向列相液晶共聚物的制备及液晶性能的研究

合成了向列相液晶单体4-乙氧基苯甲酸-4’-烯丙氧基联苯酯(M1)和胆甾相液晶分子4-(4-烯丙氧基苯丙酰氧基)-苯基苯氧羰基戊酸胆甾醇酯(M2),把液晶分子根据不同的浓度配比分别和聚甲基含氢硅氧烷接枝共聚,合成了具有不同化学结构和性能的侧链型液晶聚合物。并利用红外光谱(FT-IR)、热失重分析(TGA)、差示量热扫描分析(DSC)、偏光显微法(POM)和旋光仪等测试手段对其迚行了表征。结果表明:随着单体M2含量的增加,聚合物的比旋光度随之增加;熔融温度和清亮点随M2含量的增加而降低;偏光照片显示P1为典型的向列相液晶;M2液晶分子引入后,P2-P7为典型的胆甾型液晶。     

聚硅氧烷侧链胆固醇酯液晶聚合物的合成及性能研究

设计、合成了一种烯丙氧基联苯甲酸胆固醇酯液晶单体(V1OBEG),并通过巯基-乙烯基点击加成反应,将其接枝到聚(3-巯丙基甲基硅氧烷)(PMMS)上,得到一种新型的以聚硅氧烷为主链的侧链高分子液晶(PMMS-V1OBEG)。通过红外光谱、核磁共振氢谱、差示扫描量热仪和偏光显微镜分别对液晶单体和聚合物的分子结构及液晶行为进行表征。结果表明,液晶单体的熔点和清亮点分别为189.37℃和277.99℃,在升温过程中先后出现胆甾相的玫红色油丝织构和蓝色油丝织构,继续升温时呈指纹织构,降温过程中出现焦锥织构;聚合物的玻璃化转变温度和清亮点分别为103.71℃和278.16℃,在升温过程中出现胆甾相液晶,降温过程中无液晶相。     

聚硅氧烷侧链胆固醇酯液晶聚合物的合成及性能研究

设计、合成了一种烯丙氧基联苯甲酸胆固醇酯液晶单体(V1OBEG),并通过巯基-乙烯基点击加成反应,将其接枝到聚(3-巯丙基甲基硅氧烷)(PMMS)上,得到一种新型的以聚硅氧烷为主链的侧链高分子液晶(PMMS-V1OBEG)。通过红外光谱、核磁共振氢谱、差示扫描量热仪和偏光显微镜分别对液晶单体和聚合物的分子结构及液晶行为进行表征。结果表明,液晶单体的熔点和清亮点分别为189.37℃和277.99℃,在升温过程中先后出现胆甾相的玫红色油丝织构和蓝色油丝织构,继续升温时呈指纹织构,降温过程中出现焦锥织构;聚合物的玻璃化转变温度和清亮点分别为103.71℃和278.16℃,在升温过程中出现胆甾相液晶,降温过程中无液晶相。     

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.     

浅析热分析技术在氟聚合生产中的应用

对热分析技术进行了概括和介绍,并针对常用的差示扫描量热法（DSC）与热重分析法（TGA）在聚合物及相关领域的应用展开论述,重点分析了DSC在熔点、比热容、玻璃化转变温度等方面以及TGA在失重分析、催化剂的组分确定等方面的应用。     

含氟甾体液晶研究

以含氟基团改造3β及17β位置的端基短链,研究结构与液晶性的关系,利用液晶核的碳原子手性结构,开发胆甾相含氟液晶,探讨开发胆甾相液晶材料的可能性。将氟代芳基和全氟烷基等含氟官能团引入甾类液晶的3β-取代基中,以考察对构效关系的影响;利用的猪去氧胆酸是易得的天然甾体之一,能较为便捷地转化为具有平面构型的3β-羟基-5-胆烯酸,通过不同的方法改造其17-侧链,可考察不同基团对其构效关系的影响。以附有加热台的偏光显微镜及差示扫描量热法用来分析液晶相变化。结果发现有多种高清亮点的含氟胆甾相液晶可作为胆甾相液晶混合物的添加剂使用。     

含薄荷醇的席夫碱类蓝相液晶的合成及性能研究

设计合成了一系列以左旋薄荷醇为手性中心的新型手性液晶化合物Mt4BIAnB(n=1、2、3、4、5、6,n为末端链长)。通过红外光谱、核磁共振氢谱、差示扫描量热仪、偏光显微镜和紫外可见分光光度计分别对其结构及液晶行为进行表征。结果表明:对于该系列化合物,Mt4BIAnB(n=1、2、4)升温时无液晶性,为单变液晶。而其他化合物为互变液晶,在升温过程中呈现具有选择反射特性胆甾相油丝织构。降温过程中,该系列化合物均先后呈现小块状的蓝相织构和胆甾相的焦锥织构,并且各向同性相(Iso)向胆甾液晶相(N*)的转变温度(T_(iso-N*))呈现明显的奇偶效应,末端基为奇数的液晶化合物T_(iso-N*)高于偶数的液晶化合物。     

一种新的可生物降解聚碳酸酯的合成与表征

以天然氨基酸(L-酪氨酸)为原料合成环二肽,以环二肽为单体用光气法合成了属于拟聚氨基酸的聚碳酸酯,该聚合物的结构特点为主链肽键与非肽键重复排列,其主链结构中既有水解键又有酶解键。差示扫描量热法、热重分析法和凝胶渗透色谱法的分析结果显示,聚合物的玻璃化转变温度低于100℃,热降解温度在300℃以上,聚合物多分散度为1.338。X射线衍射结果表明,合成的聚合物为无定形物。     

Synthesis and properties of photochromic cholesteric liquid crystalline polysiloxane containing chiral mesogens and azobenzene photochromic groups

A series of novel thermotropic side‐chain liquid crystalline polymers(P₀–P₁₂) were synthesized by grafting copolymerization of mesogenic monomer cholesteryl undecylenate (M1) and photochromic monomer 4‐allyoxy‐4′‐nitroazobenzene (M2) on polymethylhydrosiloxane. The chemical structures of polymers were characterized by infrared (IR) and ultraviolet (UV) spectroscopy. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to measure the thermal properties of those polymers, and the mesogenic properties were characterized by polarized optical micrograph, DSC, wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The glass transition temperatures (T_gs) of the polymers increased from P₀ to P₄ and decreased from P₅ to P₁₂. The clearing point temperatures (T_is) of the polymers P₁–P₁₂ were lower than that of P₀, but increased from P₁ to P₄ and decreased from P₅ to P₁₂. They showed thermotropic liquid crystalline properties in a broad mesogenic region at temperatures >100°C. The polymers P₀–P₈ exhibited a cholesteric mesophase with oily streaks and lined texture, and polymers P₉–P₁₂ showed a chiral smectic mesogenic phase with a layered texture. All of the polymers were thermally stable to ～ 320°C. The UV‐induced trans–cis photoisomerization was investigated for the azo monomer and polymers P₈ and P₁₂. The solution of the azo monomer and liquid crystalline polymers P₈ and P₁₂ can undergo photoisomerization, and the environments of the azo group were responsible for the aforementioned photochemical process. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2155–2162, 2002     

Synthesis and characterization of optically active liquid crystalline polyacrylates containing mesogenic phenylbenzoate groups

A series of novel side chain liquid crystalline polyacrylates with pendant chiral groups were synthesized. It was found that monomers with electron releasing -OC₄H₉ terminal groups seem beneficial for the formation of liquid crystalline phases. Copolymerization of the monomers was carried out and the physical properties of the copolymers were investigated. All synthesized polymers revealed liquid crystalline phases and appeared highly thermally stable with decomposition temperatures (T_d) at 10% weight loss greater than 384 °C and about 50% weight loss occurred beyond 442 °C under nitrogen atmosphere. Two miscible chiral compounds were also synthesized and used as chiral dopants to induce cholesteric liquid crystalline phases of polymers. Liquid crystalline phases of the polymers were investigated using DSC and XRD, and confirmed with POM technique. The optical properties of the induced cholesteric liquid crystalline polymers were investigated using UV-vis spectrometer. The appearance and the color variation of the polymer films before and after UV irradiation were also investigated. Typical helical morphology of the cholesteric liquid crystalline film was analyzed by SEM technique.     

Study on the Optical and Mesomorphic Properties of Cholesteric Side-Chain Liquid Crystalline Elastomers Containing a Nematic Cross-Linking Agent

To study the effect of the content of the nematic cross-linking units on the mesophase behaviors, the optical and mesomorphic properties of liquid crystalline elastomers (LCEs), aseries of LCEs have been synthesized by hydrosilylation reaction with poly(methylhydrogeno)siloxane, a cholesteric liquid crystalline monomer, and a nematic cross-linking agent. The chemical structures and properties of the synthesized LCEs have been investigated by use of various techniques. Homopolymer P₀ bearing only cholesteric component displays a smectic A phase, but elastomers P₁-P₅ containing different content of nematic cross-linking units show a cholesteric mesophase. The reflection wavelengths of theLCEs show a weak temperature dependence at lower temperatures but a strong temperature dependence at higher temperatures. Furthermore, the maximum reflection wavelengths of the LCEs can be stabilized over a wide temperature range when the LCEs are heated, suggesting that the helical structure and pitch of the cholesteric phase can be stabilized with a polymer network.     

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     

Effect of the length of the carbochain on the phase behavior of side‐chain cholesteric liquid‐crystalline elastomers

In this study, we prepared two series of new side‐chain cholesteric liquid‐crystalline elastomers (PI and PII) derived from the same chiral bisolefinic crosslinking units and different nematic liquid‐crystalline monomers. The chemical structures of the monomers and polymers obtained were confirmed by Fourier transform infrared and ¹H‐NMR spectroscopy. The phase behavior properties were investigated by differential scanning calorimetry, thermogravimetric analysis, and polarizing optical microscopy. The effect of the length of the carbochain on the phase behavior of the elastomers was investigated. The polymers of the PI and PII series showed similar properties. Polymer P₁ showed a nematic phase, P₂–P₇ showed a cholesteric phase, and P₄–P₇, with more than 6 mol % of the chiral crosslinking agent, exhibited a selective reflection of light. The elastomers containing less than 15 mol % of the crosslinking units displayed elasticity, a reversible phase transition with wide mesophase temperature ranges, and a high thermal stability. The experimental results demonstrate that the glass‐transition temperatures first decreased and then increased; the isotropization temperatures and the mesophase temperature ranges decreased with increasing content of crosslinking agent. However, because of the different lengths of the carbochain, the glass‐transition temperatures and phase‐transition temperatures of the PI series were higher than those of the PII series, and the PI and PII elastomers had their own special optical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1204–1210, 2005     

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 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     

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.