聚合物分散液晶PMMA-5CB的制备及电光性能

以聚合引发相分离的方法制备了聚甲基丙烯酸甲酯(PMMA)基聚合物分散液晶(PDLC).通过差示量热扫描仪(DSC)、偏光显微镜(POM)对不同液晶5CB(4-氰基-4'-戊基联苯)含量的PDLC热力学行为和液晶分散状态进行了表征.在电压为0～30 V、波长为633 nm处,用紫外可见分光光度计(UV-Vis)对PDLC的电光性能进行了研究.结果表明当w(5CB)达到20%以上时,PDLC发生相分离现象;当w(5CB)=30%时,液晶的分散状态最佳,电光效应最强.     

多官能Iniferter制备聚合物分散液晶膜及其含量对电光性能的影响

采用可逆加成-断裂链转移(RAFT)、引发转移终止(Iniferter)活性自由基聚合法分步骤制备多官能Iniferter的大分子(RAFT-MI),并通过紫外光聚合诱导相分离法制备接枝共聚物为基体的聚合物分散液晶(PDLC)膜,研究了不同含量的RAFT-MI对PDLC膜的微观形貌、开态透光率、阈值电压(Vth)、饱和电压(Vsat)、对比度和记忆效应的影响.结果表明,当PDLC中的RAFT-MI含量从10%增加到30%时,开态透光率先增加,随后又逐渐降低,而Vth、Vsat逐渐降低,对比度先增加,然后又降低,记忆效应减弱.     

聚合物分散液晶膜

聚合物分散液晶膜是将液晶和聚合物结合,得到的一种综合性能优异的膜材料,液晶分子赋予了聚合物分散液晶膜显著的电光特性,使其受到了广泛的研究,并有着广阔的应用前景。而聚合物作为成膜材料,起着辅助但是重要的作用,其结构和固化过程是影响聚合物分散液晶膜电光特性的重要因素。本文简要综述了聚合物分散液晶膜的制备方法、电光特性的影响因素及研究手段。     

基于偶氮液晶的PDLC膜光调制研究

采用聚苯乙烯和光敏混合向列液晶(5CB＋BMAB), 通过溶剂引发相分离制备了聚合物分散液晶膜(PDLC). 利用偶氮液晶的光致相变, 实现了聚合物分散液晶薄膜的光控开关. 实验结果表明, 在PDLC膜内部液晶微球中, 液晶分子呈双极形分布. 其光控温度区间19～36 ℃之间. 以360 nm附近紫外光照射之后, PDLC膜的最大透光率从6%增加到93%. 在相同的工作距离下, 光调制的时间与PDLC膜内部微孔直径相关. 在相同的液晶浓度下, 直径越小, 调制时间越长.     

聚合物分散液晶单体4,4′-二[6-(丙烯酰氧基)己氧基]联苯的合成

利用丙烯酰氯代替丙烯酸钾与4,4′-二(6-溴己氧基)联苯反应改进了制备4,4′-二[6-(丙烯酰氧基)己氧基]联苯(BAB6)的合成路线。改进前的反应温度较高,中间产物溶解度小,产物呈淡黄色,收率仅12.4%;改进后在室温反应,中间产物溶解度较高,产物呈白色,收率达到46.8%。采用1HNMR、13CNMR和元素分析对中间体和BAB6结构进行了表征。由改进后合成的单体,制备了具有快速响应的聚合物分散液晶(PDLC)膜,响应时间约2ms。扫描电子显微镜观察的结果表明,PDLC中形成了聚合物网络结构。     

紫外光固化PDLC膜性能的温度效应

考察了紫外光固化PDLC膜的电光性能及其温度依赖性,阐述了其作为显示器件的工作稳定性。指出确定PDLC工作温度范围的方法,对PDLC膜中液晶相的N-I转变行为及其与膜的内部结构的关系进行了讨论。     

丙烯酸酯/液晶体系的光聚合反应动力学对PDLC电光性质的影响

采用光-示差扫描量热法(P-DSC)和光-流变学(P-Rheology)技术,测定了丙烯酸酯/液晶体系的光聚合反应动力学和凝胶化时间.基于自催化模型和凝胶时间-温度关系,计算了体系的光聚合反应速率常数和活化能,探讨了单体结构与组成、反应温度对体系光聚合动力学的影响,并研究了聚合物分散液晶(PDLC)的电光响应行为与相分离结构对光聚合动力学的依赖性.结果表明,升高反应温度、增加体系的单体反应活性和平均官能度,均提高了体系的光聚合速率常数,缩短了光聚合凝胶时间.随着单体反应活性和平均官能度的提高,体系的光聚合反应活化能明显降低,且凝胶化前的光聚合反应活化能低于光聚合全过程的平均反应活化能.当液晶含量为50%时,形成的PDLC呈亚微米尺度的双连续相结构.随着光聚合反应温度的升高,光聚合速率加快,导致凝胶时间缩短、相分离程度降低,使PDLC中液晶相尺寸变小、聚合物网络致密化,PDLC的弛豫时间延长、饱和电压降低,而开启时间和阈值电压变化不大.     

大分子引发剂分子量对接枝聚合物基体的PDLC电光性能的影响

以可逆加成-断裂链转移(RAFT)、引发转移终止(iniferter)活性自由基聚合相结合的方法,用一步法制备了不同分子量的大分子引发剂RAFT-PS-co-PCMSI(MI),并通过紫外光聚合诱导相分离法制备了以接枝聚合物为基体的聚合物分散液晶(PDLC)膜.研究了不同分子量的MI对PDLC的微观形貌,关闭状态透光率,阈值电压,饱和电压以及记忆效应等方面的影响.研究表明,降低PDLC中MI的分子量,会使得液晶微滴粒径增大,阈值电压(Vth)、饱和电压(Vsat)减小,记忆效应、关闭状态透光率升高.     

醚链改性聚环氧乙烷的合成及性能研究

考察烷基磷酸铝催化剂i-Bu₃Al/H₃PO₄/DBU催化环氧乙烷(EO)、甘醇甲基缩水甘油醚(nGE)与烯丙基缩水甘油醚(AGE)二元及三元共聚合的催化性能,通过核磁共振波谱(NMR)、凝胶渗透色谱(GPC)和示差扫描量热仪(DSC)对共聚物微观结构和热性能进行表征分析。结果表明25℃甲苯溶剂中,i-Bu₃Al/H₃PO₄/DBU催化剂可以高效催化不同比例的EO、nGE和AGE共聚合,以100%收率获得组成精确可控的高分子量EO-nGE二元及EO-AGE-nGE三元无规共聚物;nGE的醚链长度对聚合性能无影响,二甘醇甲基缩水甘油醚(2GE)和四甘醇甲基缩水甘油醚(4GE)均可实现可控引入聚环氧乙烷制备醚链改性聚环氧乙烷。EO-AGE-nGE三元共聚物以1,2-乙二硫醇为交联剂制备了交联聚合物。测试醚链改性聚环氧乙烷的性能,发现醚链长度、含量及交联对聚合物电导率和力学性能有很大影响。4GE为共聚单体的聚环氧乙烷电导率高于2GE。随着醚链含量增大,聚合物电导...     

由聚丙二醇二缩水甘油醚和甘油制备温敏性超支化聚合物

由聚丙二醇二缩水甘油醚和甘油通过质子转移聚合(proton transfer polymerization)一步法制备了端羟基的温敏性超支化聚醚.聚合产物的分子量(Mn)在1.76×104~2.43×104之间,玻璃化转变温度(Tg)在-31.5~-26.7℃之间,热分解温度(Td)在367~376℃之间.通过控制聚丙二醇二缩水甘油醚和甘油的投料比,实现了对温敏性超支化聚醚最低临界溶解温度(LCST)的调节,LCST可控制在28.3~39.6℃之间.     

The physical properties of alkene-terminated liquid crystal molecules/E8 mixture and the electro-optical properties as they doped in polymer-dispersed liquid crystal systems

Effects of the content of fluorinated alkene-terminated liquid crystal (LC) molecules on the physical properties of the fluorinated alkene-terminated LC/E8 mixture were studied. The morphology and electro-optical properties as they doped in polymer-dispersed liquid crystal (PDLC) films were investigated. The detailed discussion of the obtained results is given. As a result, comparing with the physical properties of the series of LC mixtures with the same content of the analogous fully saturated compounds doped with E8, we find that the birefringence is significantly larger for the LC mixture with the alkene-terminated materials. Both fluorinated alkene-terminated LC molecules and the analogous fully saturated compounds doped with E8 reduce the driving voltage of PDLC films. Moreover, PDLC films with the fluorinated alkene-terminated LC molecules possessed higher contrast ratio and faster response time than that of the PDLC films prepared by adding the same mass fraction of the analogous fully saturated compounds. Thus, the ability to manipulate physical properties of LC mixture and electro-optical properties of PDLC films by changing the LC molecular structures may have future relevance for new LC structures design and applications of PDLC films.     

Cyano terminated tolane compounds for polymer dispersed liquid crystal application: relationship between cyano terminated tolane based molecular structures and electro-optical properties

ABSTRACT

The structures of the liquid crystal (LC) molecules have a key role in impacting the electro-optical performance of a polymer dispersed liquid crystal (PDLC) film. In this paper, the relationship between the LC molecular structures and the electro-optical properties of PDLC films is investigated based on an unexplored cyano-terminated tolane compounds (CTTCs) doped E8 LCs/UV polymers system. Due to the high polarity of CTTCs, LCs doped with the cyano-terminated tolane (CTT) molecules exhibit high birefringence and large positive dielectric anisotropy. On the whole, PDLC films doped with the CTT molecules exhibit a lower driving voltage than that doped with the pure E8. More excitingly, PDLC films based on CTT molecules with larger length-to-width ratio and longer conjugated system show higher contrast ratio (CR) and faster response time. Eventually, the mechanism of the effects of CTT-based molecular structures and the relationship between the electro-optical performance of PDLC films and CTT molecules are illustrated. This work paves a new way for optimising the electro-optical properties of PDLC films.     

Comparative studies of polymer‐dispersed liquid crystal films via a thiol‐ene click reaction

In this work, the thiol‐ene click reaction is employed to fabricate polymer‐dispersed liquid crystal (PDLC) films by photoinitiated polymerization. The PDLC films are prepared by systematic variation of key conditions: variety and content of ‐ene monomer, liquid crystal (LC) content, curing time, and curing light intensity. We find that both the morphologies and electro‐optic properties of these films are adjustable. When increasing the length of alkyl main chain of ‐ene monomers, the driving voltages reduce, but in turn, the contrast ratio decreases. Increasing ‐ene monomer content raises the driving voltages as well as the response time, and the increase of LC content lowers the driving voltages but has a negative effect on the contrast ratio. The changes to the curing conditions (both curing time and UV light intensity) can be used to modify the driving voltages, response time, and contrast ratios of PDLC films. These comparative studies will elucidate new insights in commercial applications of intelligent PDLC films.     

A study on the polymer structures and electro-optical properties of epoxy-mercaptan-based polymer dispersed liquid crystal films

ABSTRACT

In this paper, polymer dispersed liquid crystal (PDLC) films based on epoxy-mercaptan system were prepared by thermal-initiated polymerization. The effects of the liquid crystal (LC) content, the proportion and the functionality of epoxy monomers on the polymer structures and electro-optical properties of the as-made PDLC films were investigated systematically. It was found that the morphologies of the polymer matrix can be altered from polymer meshes to polymer balls by increasing the LC content as well as the functionality of epoxy monomers. Accordingly, the electro-optical properties could be regulated by the morphologies of polymer networks. Especially, the as-made PDLC films with homogeneous porous structures exhibited the optimal electro-optical properties. Consequently, this work offers a meaningful approach to control the microstructures and optimize the electro-optical properties of PDLC films, which indeed can form a wonderful footstone for the wide application of PDLC.     

Effects of thiol monomers on the electro-optical properties of polymer-dispersed liquid crystal films prepared by nucleophile-initiated thiol-ene click reaction

ABSTRACT

Nucleophile-initiated thiol-ene click reaction is a highly novel and efficient method of preparing polymer-dispersed liquid crystal (PDLC) films. The effects of thiol monomers on the electro-optical properties of PDLC films prepared by nucleophile-initiated thiol-ene click reaction were investigated in this work. The thiol monomers were dithiol, trithiol, tetrathiol or their mixture. It was found that the increase of functionality could lead to the increase of threshold voltage and saturation voltage and the decrease of off-state transmittance. The influence of reaction temperature was also investigated. The results indicated that functionality and reaction temperature had combined effects on the electro-optical properties of PDLC films.     

Thermo-mechanical and electro-optical properties of polymer dispersed liquid crystal films

We have observed a strong dependence of the electro-optical properties of polymer dispersed liquid crystal (PDLC) films on temperature. One plausible explanation for this dependence is the thermal expansion of the films. We investigated the thermal expansion of various PDLC films using a thermal mechanical analyser (TMA). As the temperature increased, the films expanded and their droplet size decreased, and their contrast, response time, and hysteresis changed simultaneously. We observed obvious changes of thermal expansion coefficient of the films. We studied the qualitative relationship between thermo-mechanical properties and electrooptical properties. The thermal expansion of PDLC films could be adjusted by changing the degree of cross-linking of the polymer.     

Complex study of reorientational dynamics of the liquid crystal in PDLC films

Morphological, electro-optical and switching properties of polyester resin/nematic liquid crystal composite films have been studied for varying composition (10-40 wt% of LC), temperature (20-50 C), film thickness (10-75 mum) and UV curing time of the matrix (0.25-12 min). The PDLC films were formed by LC separation in a UV polymerization process of the thin layer of oligoester resin (liquid crystal mixture) between ITO coated glass plates. The electro-optical and response behaviour based on the electric field controlled light scattering of the composite films was observed. The results were interpreted in terms of effective anchoring strength at the interface of the polymer and liquid crystal depending either on the area fraction of the interface in the composite film (dependent on the size and shape of the liquid crystal droplets) or the stiffness and resistivity of the polyester resin changing in the course of the crosslinking polymerization.     

Control of the microstructure of polymer network and effects of the microstructures on light scattering properties of UV‐cured polymer‐dispersed liquid crystal films

Polymer‐dispersed liquid crystals (PDLC) films were prepared from ultraviolet (UV) irradiation‐induced polymerization of the photopolymerizable monomers in photopolymerizable monomers/nematic liquid crystal (LC) mixtures. The effects of the composition of the mixtures, the curing temperature, and the UV light intensity on the microstructure of the polymer network in the PDLC films were investigated. Furthermore, the effects of the microstructures on the light scattering properties of the PDLC films in the wavelength region of 300–2500 nm were studied experimentally and theoretically based on the combination of three kinds of classical light scattering theories: the Rayleigh‐Gans (RG) approach, the anomalous diffraction (AD) approach, and the geometrical optics (GO) approach. It was found that the sizes of LC domain in PDLC films increased with the increase of the LC content as well as the decrease of the UV curing intensity, while increased at first and then decreased with the increase of the curing temperature. Moreover, smaller LC domain sizes could exhibit strong scattering properties in a smaller VIS wavelength region and the transmittance in NIR region (especially in the wavelength range of 1300–2500 nm) obviously decreased with the increasing sizes of LC domain. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2090–2099, 2008     

Effects of alkyl chain length of monomer and dye-doped type on the electro-optical properties of polymer-dispersed liquid crystal films prepared by nucleophile-initiated thiol-ene click reaction

ABSTRACT

Polymer-dispersed liquid crystal (PDLC) films containing a series of monomers with different alkyl chain lengths were prepared by nucleophile-initiated thiol-ene click reaction. The effect of alkyl chain length of monomers, dye and temperature on electro-optical properties of PDLC films was investigated. It was found that the alkyl chain length and polymerisation rate of monomers together determine the size of liquid crystal (LC) droplets, thus affecting the electro-optical properties of PDLC. In addition, the type and content of dyes could be optimised to obtain PDLC materials with better comprehensive properties for display.     

TSC study and electro‐optical properties of epoxy/acrylic polymer‐dispersed liquid‐crystal film in DICY thermal cure

We report on the structures and electro‐optical properties of epoxy/acrylic polymer‐dispersed liquid‐crystal (PDLC) films. A thermal stimulated current (TSC) analysis was used to investigate the physical structures of PDLC. In the TSC spectrum of PDLC, three relaxation peaks were observed: the glass transition of the liquid crystal, the glass transition of the polymer matrix, and the ρ transition. The ρ transition represents the discharge behavior of space charges, and its intensity increased as the curing time and content of the curing agent dicyandiamide (DICY) increased. The pre‐UV‐cured films with different DICY contents were thermally cured at 130 °C for various periods. The electro‐optical properties of PDLC, such as the contrast ratio and switching voltage, increased as the curing time of DICY, the content of DICY, or both increased. As the ambient temperature increased from 10 to 40 °C, the contrast ratio and switching voltage of PDLC gradually decreased. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 507–514, 2001