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.     

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.     

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.     

固化条件对聚合物分散液晶膜电光性能的影响

选用聚乙二醇二缩水甘油醚(EGDE)/季戊四醇缩水甘油醚(PERTGE)/1,8-二氨基-3,6-二氧杂辛烷(EDBEA)/向列相液晶(SLC1717)复合体系,在不同的固化条件下,通过热聚合诱导相分离方法制备了一系列电光性能不同的聚合物分散液晶(polymer dispersed liquid crystal,简称PDLC)膜.研究了固化温度和固化时间对制备的PDLC膜中聚合物网络的微观形貌和电光性能的影响.结果表明,随着固化温度的升高以及固化时间的缩短,PDLC膜的对比度、驱动电压和开态响应时间逐渐增大,而关态响应时间逐渐减小.在固化温度为363.2 K,固化时间为7 h时,所制备的PDLC膜具有较佳的电光性能.     

不同醇对聚合物分散液晶光聚合动力学及其电光特性的影响

以丙烯酸-2-乙基己酯(EHA)、二甲基丙烯酸乙二酯(EDMA)/季戊四醇四丙烯酸酯(PETTA)为混合单体、液晶P0616A为液晶相、Irgacure 184为光引发剂,通过UV光引发制备了聚合物分散液晶(PDLCs),研究了不同烷基链长醇,即乙醇(EtOH)、正丁醇(nBA)、正己醇(nHA)、正辛醇(nOA)和正十四醇(nTA)对体系光聚合动力学及其PDLCs液晶相变温度及电光特性的影响.结果表明引入醇分子显著加快了丙烯酸酯/液晶复合体系的光聚合反应速率,提高了单体的最终转化率,其中以正丁醇体系最为明显.随着醇分子烷基链的增长,体系的转化率趋于降低,但依然明显高于不含醇的体系.醇分子的加入降低了PDLCs中液晶相的TNI,且随着醇分子烷基链长的增长,PDLCs液晶相的TNI总体上呈降低的趋势.醇分子的加入增加了PDLCs液晶微区中向列相液晶的含量,而含正丁醇和正十四醇的体系液晶微区中向列相液晶低于其它3个含醇体系.醇分子的加入明显降低了PDLCs的阈值电压和饱和电压以及对比度.结合体系的光聚合速率和单体转化率,正丁醇是改善PDLCs性能的最佳选择.     

RAFT聚合合成高分子量嵌段聚合物

以合成高分子量聚合物为目标,以苯基二硫代乙酸-1-苯基乙酯(PEPDTA)作为RAFT试剂,研究引发剂的种类(偶氮二异丁腈(AIBN)、1-1′-偶氮环己腈(ACC))、用量及聚合温度对苯乙烯/丙烯酸丁酯RAFT共聚合过程和聚合物结构的影响.结果发现,由于体系中RAFT浓度很低,相应的引发剂浓度要比传统自由基聚合低得多,只有采用较高的聚合温度和低分解速率常数的引发剂(ACC),才能制得无活性聚合物分率低(<0.1)、分子量高的聚合物,并进一步得到杂质含量少、分子量分布窄的嵌段聚合物.     

分子印迹聚合物的制备及孔结构研究

以N 叔丁氧羰酰 L 色氨酸和N 叔丁氧羰酰 L 酪氨酸为印迹分子 ,分别采用光引发聚合和热引发聚合制备了分子印迹聚合物 ,并对聚合物的手性识别能力进行了色谱评价 .结果表明 ,制备的分子印迹聚合物对印迹分子具有特异性的吸附作用 ,光引发聚合的N 叔丁氧羰酰 L 色氨酸的印迹聚合物对印迹分子的选择性因子达到 2 .318,热引发聚合的N 叔丁氧羰酰 L 酪氨酸对印迹分子的选择性因子为 1 373 进一步研究了分子印迹聚合物的孔结构 ,发现光引发聚合的分子印迹聚合物与空白聚合物的孔结构差别比热引发聚合的分子印迹聚合物与空白聚合物的差别更为明显 .对印迹分子洗脱前后的印迹聚合物的孔结构研究进一步表明 ,印迹分子存在于不同类型的孔中 .     

聚合物分散液晶(PDLC)材料的光聚合反应

以Ar+激光器为光源, 采用虎红、 N-苯基甘氨酸、二季戊四醇羟基五丙烯酸酯和乙烯基吡咯烷酮分别作为光引发剂、共引发剂、预聚物和稀释剂, 与液晶材料TEB30A结合, 通过光聚合反应, 制备了聚合物分散液晶(PDLC), 用紫外光谱和荧光光谱对其反应机理进行了分析. 实验结果表明, PDLC是通过光引发剂吸收光子能量后与共引发剂相互作用, 形成自由基中间体并引发聚合反应, 使预聚物与液晶产生相分离形成的.     

用大分子引发剂法制备嵌段共聚物

主要介绍了用大分子引发剂法制备嵌段共聚物的方法。大分子引发剂是从已商品化的功能聚合物制得或用其它活性聚合方法合成。从单封端的端羟基聚合物、其它单官能团或双官能团聚合物以及双功能基团缩聚物制得大分子引发剂．然后用于原子转移自由基聚合(ATRP)、氮氧稳定自由基聚合以及可逆加成裂解链转移(RAFT)聚合等．可制得结构可控、分子量分布窄的嵌段共聚物。     

A novel polymer dispersed liquid crystal film prepared by reversible addition fragmentation chain transfer polymerization

Polymer as an important component of polymer dispersed liquid crystal (PDLC) has a great influence on electro-optical properties. In this letter, the effect of molecular weight of polymer matrix on the electro-optical properties of PDLC films was investigated with reversible addition fragmentation transfer (RAFT) polymerization. It was found that the saturation voltage and memory effect were apparently influenced by molecular weight of polymer which can be regulated efficiently by irradiation time, while the morphology of liquid crystal droplets kept unaltered. It was estimated that the increase of molecular weight of polymer enhanced entanglement between polymer and liquid crystal, which induced the different surface interaction and electro-optical properties.     

The effect of molecular weight of polymer matrix on properties of polymer-dispersed liquid crystals

The electro-optical properties and memory effects are important characters of polymer-dispersed liquid crystal (PDLC) devices. Molecular weight of polymer matrix influences the morphology of liquid crystal droplets in PDLC film and the performance of PDLC devices. In this letter, PDLC films were doped with a small amount of chain transfer agent (CTA), in order to control the molecular weight of polymer matrix. It is observed that the addition of CTA induces a reduction of threshold voltage. In addition, the effect of molecular weight on memory effects of PDLC devices was also discussed. It is found that the entanglement between polymer and liquid crystal molecule increased with the molecular weight, which reduces the memory effect.     

Effect of molecular weight of macro‐iniferter on electro‐optical properties of polymer dispersed liquid crystal films prepared by iniferter polymerization

Polymer dispersed liquid crystal (PDLC) films were prepared by a devised method, in which photo‐polymerization induced phase separation in a mixtures of a macro‐iniferter, methyl acrylater, and liquid crystal. The morphology of the obtained PDLC films was examined on a polarized optical microscopy, and the effect of molecular weight of MIs on the electro‐optical properties was deliberately investigated. Decreasing the molecular weight of MIs in the films led to formation of larger liquid crystal droplets and a lower V_th values. V_sat increased and the memory effect decreased because of the increased interface anchoring strength induced by the higher molecular weight of polymer matrices. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1530–1534, 2009     

Study on the electro-optical properties of polyimide-based polymer-dispersed liquid crystal films

The reflectivity control device, initially developed for attitude control, is utilised to control the solar sail orbit by switching the states between absorption and specular reflection. Actually, the major parts of the device are the polymer-dispersed liquid crystal (PDLC) films. Here, PDLC films based on polyimide (PI) as polymer matrix and a low molecular weight LC can be prepared by the thermally induced phase separation (TIPS) method. The influences of cooling rate and the content of LC on the size and uniformity of LC droplets dispersed in a polymer matrix by a TIPS process were investigated. It was found that a fast cooling rate gave smaller droplet sizes and hence a more uniform distribution as compared to the ones produced under a slow cooling rate. If the LC content was increased, the droplet size would be increased. Furthermore, the effect of LC droplet size on the electro-optical properties of the PI-based PDLC films was discussed, such as transmittance, threshold voltage, driving voltage and contrast ratio (CR).     

Improvement of permanent memory effect in PDLC films using TX-100 as an additive

A number of polymer dispersed liquid crystal (PDLC) films based on dimethacrylate monomers were synthesised by polymer-induced phase separation (PIPS) using polyethylene glycol p-(1,1,3,3-tetramethylbutyl)-phenyl ether (TX-100) as an additive up to total solution weight of 10% aiming to modify the initial anchorage force of the liquid crystal (LC) molecules to the polymeric matrix. The effects of the addition of this additive to the PDLC films were studied resorting to electro-optical studies. Using a fitting model, several parameters were correlated such as the permanent memory effect (PME), the voltage required to achieve 90% of maximum transmittance (E90), the average elastic constant (K) and the rotational viscosity of the director (γ). The use of TX-100 results on an increase on the PME and γ, and decrease on the E90 and K.     

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.     

The effect of the resultant microphase-separated structures of polymer matrices on the electro-optical properties of polymer dispersed liquid crystal films by Iniferter polymerization

Iniferter polymerization was employed to prepare polymer dispersed liquid crystal (PDLC) films and an additional photoinitiator was introduced to induce the phase separation of polymer matrices themselves on the process of preparing the PDLC. The effect of the polymerization kinetics and the resultant microphase-separated structures of polymer matrices on the electro-optical properties of PDLC films were studied. It was found that the bigger length scale of phase separation of polymer matrices induced strong light-scattering resulting in low ON-state transmittance. And faster polymerization kinetic induced higher threshold and saturation voltages.     

Effects of crosslinking agent/diluents/thiol on morphology of the polymer matrix and electro-optical properties of polymer-dispersed liquid crystal

To study effects of the crosslinking agent/diluents/thiol on morphology of the polymer matrix and the electro-optical properties of polymer-dispersed liquid crystal (PDLC) films, samples were prepared by ultraviolet (UV)-initiated polymerisation. Due to the interaction between thiol–acrylate reaction and acrylate monomers polymerisation, the sample compositions were the foremost determinant to the microstructures which in turn played an essential role on the electro-optical properties of the PDLC films. With the increasing content of the crosslinking agent, the LC droplet size decreased, while the thiol had a contrary effect on the LC droplet size. It was demonstrated that the superior properties of the low-driven voltage (37.2 V), the high contrast ratio (148.2), the short response time (14.9 ms) and the high saturation transmittance (86.6%) could benefit from a novel microstructure which had a dense surface and meshes with microspheres attached. It was of great significance for the optimisation and the potential applications of the PDLC films.     

The investigation of molecular affinity involved in poly(ethylene glycol)-based polymer-dispersed liquid crystal display

Acrylic polyethylene glycol(PEG)-based polymer-dispersed liquid crystal (PDLC) films have been fabricated to investigate the effect of intermolecular interactions on PDLC performance. For this purpose, the amphiphilic liquid crystal and polymers are selected as PDLC composite materials. The acrylic PEG contents are varied from 0 to 66.66 mol wt.% in order to understand the effects of different levels of additions on the microstructure and electro-optical properties of the PDLC films. For this intention, polarized optical microscopy and UV–vis spectroscopy are used. The extent of phase separation and anchoring energy are also examined using Fourier transform infrared (FTIR) spectroscopy and contact angle measurements in consequence of acrylic PEG addition. The contrast ratio, threshold voltage, as well as saturation voltage, tended to increase with the addition of acrylic PEG. The molecular affinity involved in the polymer matrix and LC molecules affected the phase separation which is responsible for the formation of domain size; this accordingly changed the electro-optical properties of PDLC film.