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.     

Effects of functionality of thiol monomer on electro-optical properties of polymer-dispersed liquid crystal films

In this paper, polymer-dispersed liquid crystal (PDLC) films which based on the acrylate and the thiol monomers were first prepared by ultraviolet-initiated polymerisation. The electro-optical properties and morphologies of the PDLC films were systematically investigated. The functionality of thiol monomers and their feed ratio showed great influence on the properties of the fabricated PDLC films because of the existence of competition between thiol–acrylate reaction and acrylate monomer polymerisation reaction. This made the polymer network and electro-optical properties of the PDLC films easily tunable by the introduction of the thiol monomers. When added four-functional thiol monomer PETMP with appropriate concentration into the PDLC system, lower driven voltage and higher contrast ratio were achieved.     

Facile fabrication of polymer-dispersed liquid crystal films via nucleophile-initiated thiol-ene click reaction

Nucleophile-initiated thiol-ene click reaction was employed to prepare polymer-dispersed liquid crystal (PDLC) films initiated by 4-dimethylaminopyridine (DMAP). The PDLC films were prepared in different temperature. It is found that the reaction temperature has a big influence on the electro-optical properties of PDLC films and 60°C is the optimal temperature to fabricate PDLC film which has high ON state transmittance (T_on) and low OFF state transmittance (T_off). UV-Visible spectrophotometer, scanning electron microscopy and polarised optical microscope were employed to explore the obtained PDLC films. Nucleophile-initiated thiol-ene click reaction, without UV-light, probably provides a new pathway to prepare 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.     

Fabrication of dye-doped polymer-dispersed liquid crystals with low driving voltage based on nucleophile-initiated thiol-ene click reaction

Dye-doped polymer-dispersed liquid crystal (PDLC) is an attractive material for application in smart windows. We report a novel dye-doped PDLC system with low driving voltage (V_dr) fabricated by nucleophile-initiated thiol-ene click reaction for the first time. The V_dr decreased significantly with the addition of monofunctional monomer. The influences of reaction temperature on the electro-optical properties of PDLC are also investigated in this work.     

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

ABSTRACT

A series of crosslinking agents with different chain lengths were used to explore their effect on electro-optical properties of dye-doped polymer dispersed liquid crystals (PDLCs) film prepared by nucleophile-initiated thiol-ene click reaction. The influences of dye contents and temperatures on electro-optical properties were also investigated. It was found that the increase in chain length of crosslinking agent leads to the increase in driving voltage and the decrease in memory effect. The decrease in reaction temperature causes a decrease in driving voltage and an increase in transmittance. Particularly, the dye content could be optimised to obtain promising materials with minimum driving voltage and high contrast ratio for display applications.     

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.     

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.     

Effects of thiol-ene click reaction on morphology and electro-optical properties of polyhedral oligomeric silsesquioxane nanostructure-based polymer dispersed liquid crystal film

Polymer dispersed liquid crystals (PDLCs) have lit a flash of interest due to the distinctive property of electrically controlled switching. However, too high-driving voltage associated with porous polymer networks always limit their wider range of applications. Herein, we reported a PDLC system containing LCs, 2,2′-(Ethylenedioxy)diethanethiol (DET) with thiol groups, cage-like nanostructure acrylic polyhedral oligomeric silsesquioxane (KH570-POSS) and KH570-SiO₂ nanoparticle modified by acrylic groups. The cage-like KH570-POSS microstructure was injected to the polymer matrix when KH570-POSS reacted with DET via thiol-ene click reaction. The morphological results demonstrated that the droplet size increased with the higher content of DET due to the decrease of the crosslink between the acrylic groups in KH570-POSS, which results in a less dense of polymer network and thus make the LC droplets easier to be driven in the electric filed. Then, a silica-based nanoparticle KH570-SiO₂ modified by acrylic groups was introduced into the system. The results indicated that KH570-SiO₂ could replace partial KH570-POSS to form the polymer network via thiol-ene click reaction, which increased the compatible ability of SiO₂ nanoparticles in the as-made film. The contrast ratio was increased to 165 when there was nearly 5 wt% content of KH570-SiO₂. Besides, the driving voltage was reduced by almost 60% and the sample could be fully driven by 30 V which is lower than the safe voltage (36 V). This study opens a route for the preparation of commercial PDLC films by thiol-ene click reaction, enabling the creation of low-voltage-driven smart windows.     

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.     

Effects of monomer structure on the morphology of polymer networks and the electro-optical properties of polymer-dispersed liquid crystal films

Polymer-dispersed liquid crystal (PDLC) films were prepared by photochemical polymerisation with a series of (meth)acrylate monomers. The effects of monomer structure on the morphology of polymer networks in the PDLC films were studied. The acrylate monomers without sidegroup chain formed uniform polymer networks. The methacrylate monomers with methyl as their sidegroup chains formed lace-like networks. The size of the LC droplets increased with increasing the length of the flexible chain of both methacrylate and acrylate monomers. Meanwhile, the effects of the morphology of the polymer network on the electro-optical properties of PDLC films were also investigated.     

Influence of chain length of prepolymers in permanent memory effect of PDLC assessed by solid-state NMR

ABSTRACT

The relationship between linear chain (ethylene oxide units) length of polymerisable monomers with morphology, electro-optical properties and ¹³C nuclear magnetic resonance (NMR) spectroscopy of the corresponding polymer-dispersed liquid crystal (PDLC) films was investigated. The preferred liquid crystal molecule alignment and permanent memory effect of PDLC were greatly influenced by the length of the molecular chain of prepolymers to be incorporated as a polymer matrix. By increasing the number of ethylene oxide in prepolymer chain and maintaining the number of functionalities (polymerisable groups in each monomer molecule), the permanent memory effect of PDLC increased, as proved by solid-state ¹³C NMR spectroscopy.     

An electrically light-transmittance-switchable film with a low driving voltage based on liquid crystal/polymer composites

ABSTRACT

As a typical class of electrically light-transmittance-switchable (ELTS) composites materials, polymer dispersed liquid crystal (PDLC) films have been widely used in displays, smart windows, light shutters, etc. However, the commercialised PDLC film still requires a comparatively high voltage to maintain its transparent state, leading to huge power consumption and even a potential safety risk. In this regard, we proposed a ‘heat followed UV’ stepwise polymerisation strategy for preparing a kind of ELTS film with a low driving voltage (~20.7 V) through constructing a coexistent system of polymer dispersed and polymer stabilised liquid crystal (PD&SLC). In this new PD&SLC system, vertically orientated polymer networks were formed within LC domains to induce the vertical alignment of LC, thereby reducing the driving voltage. Also, the as-made PD&SLC film exhibited good flexibility due to the high content of polymer. Moreover, the effects of the liquid crystalline polymerisable monomers content on the polymer morphologies as well as the electro-optical properties of the as-made PD&SLC films were elaborately investigated.     

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.     

Synthesis and nanoimprinting of high refractive index and highly transparent polythioethers based on thiol-ene click chemistry

This work demonstrates the UV nanoimprinting lithography (UV-NIL) of high refractive index and highly transparent polythioethers based on thiol-ene click chemistry. Herein, 9,9-bis(3-mercaptopropylphenylether)fluorene (BMPF) is designed as a new thiol monomer with a high refractive index, high transparency, and good processability for UV-NIL. Colorless polythioethers are synthesized from BMPF and ene monomers under mild thiol-ene click reaction conditions. Excellent transmittance (96%) of 400 nm light is observed in all the polymer films and high refractive index values of 1.5972–1.6382 are attained. UV-NIL using thiol-ene photopolymerization affords polymer nanoimprinting patterns with various features on the order of 100–500 nm without any fractures. To the best of our knowledge, this is the first report on UV-NIL of high refractive index and highly transparent polymers. Through proper monomer and polymer design, novel polythioethers with suitable glass transition temperature (T _g) values are developed with high refractive index, high transparency, and good UV-NIL processability. Furthermore, UV-NIL based on thiol-ene click chemistry is accomplished at the nanoscale. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2175–2182     

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.     

Temperature dependence of electro-optical characteristics of polymer dispersed liquid crystal films

Polymer dispersed liquid crystal (PDLC) films consist of microdroplets of a liquid crystal dispersed in a polymer matrix. Their applications are based on the electrically controllable light scattering properties of the liquid crystal droplets. The effects of temperature on the electro-optical properties of PDLC films have been rarely investigated. In this work, we studied the light transmission on varying the temperature and frequency. It was observed that the transmission at a fixed voltage decreased with increasing temperature above 43°C, independent of frequency. We examined possible origins of this unusual dependence of the transmission on the temperature. It was concluded that conductivity effects due to free ions newly created at high temperatures could be responsible for the unusual behaviour observed.     

Temperature dependence of electro-optical characteristics of polymer dispersed liquid crystal films

Polymer dispersed liquid crystal (PDLC) films consist of microdroplets of a liquid crystal dispersed in a polymer matrix. Their applications are based on the electrically controllable light scattering properties of the liquid crystal droplets. The effects of temperature on the electro-optical properties of PDLC films have been rarely investigated. In this work, we studied the light transmission on varying the temperature and frequency. It was observed that the transmission at a fixed voltage decreased with increasing temperature above 43°C, independent of frequency. We examined possible origins of this unusual dependence of the transmission on the temperature. It was concluded that conductivity effects due to free ions newly created at high temperatures could be responsible for the unusual behaviour observed.     

Effects of a chemically modified multiwall carbon nanotubes on electro-optical properties of PDLC films

Polymer dispersed liquid crystal (PDLC) films are fabricated by well-known polymerization-induced phase separation method. In this paper, the dispersion of multi-walled carbon nanotubes (MWCNT) in liquid crystals has been enhanced by chemical modification and we have investigated their effects on the morphology, electro-optical properties and conductivity of the PDLC films. Results indicated that the threshold voltage and the saturation voltage of PDLC films decreased with the increase of the doping concentration of MWCNT or chemically modified MWCNT, because carbon nanotubes can enhance the electric field by reducing the resistivity of the medium and increasing the capacitance of the cells. It can be viewed obviously that the contrast ratio of the PDLC films doped with the chemically modified MWCNT is higher than that of the MWCNT.     

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.