Structural effect of photoinitiators on electro‐optical properties of polymer‐dispersed liquid crystal composite films

Two types of photoinitiators were synthesized: (1) a α,ω‐telechelic oligomeric photoinitiator, by the reaction of poly(propylene glycol) diglycidylether (PPGDGE) and 2‐hydroxy‐2‐methyl‐1‐phenyl‐propan‐1‐one (Darocur 1173), and (2) a polymeric photoinitiator, by copolymerization of a monomer that had a liquid crystalline property, 4‐[ω‐(2‐methylpropenoyloxy)decanoxy]‐4′‐cyanobiphenyl, with a vinyl monomer that had a photosensitive group. For comparison, low‐molecular‐weight (low‐MW) photoinitiator (Darocur 1173) also was used. Attention was directed to the structural effect of the photoinitiators on the electro‐optical properties of polymer‐dispersed liquid crystal (PDLC) film in which the LC phase occupied a major volume (80 wt % of the composite film). For the preparation of PDLC films by the polymerization‐induced phase separation method, the optimum UV‐curing temperature was observed at 50°C, a temperature slightly higher than the cloud temperature (T_cloud) of the low‐MW LC/matrix‐forming material mixture. It was found that the electro‐optical performance of the PDLC cell fabricated with the oligomeric or polymeric photoinitiator was better than that of the PDLC cell made with a low‐MW photoinitiator (Darocur 1173), exhibiting lower driving voltage (V₉₀) and higher contrast ratio under identical formulation conditions. Oligomeric photoinitiators allowed premature phase separation between the LC and matrix phases, resulting in relatively pure LC‐rich phases. For the polymeric photoinitiator, incorporation of mesogenic moieties into the photoinitiator resulted in not only a well‐defined LC/matrix morphology but also in low driving voltage (V₉₀) because of reduced friction at the LC/matrix interfaces. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 162–169, 2006     

The improvement of electro‐optical properties of polymer‐dispersed liquid crystals with graft copolymer matrix synthesized by reversible addition–fragmentation chain transfer and atom transfer radical polymerization

Aiming to decrease the memory effect of polymer‐dispersed liquid crystals (PDLCs), a type of graft macroinitiator, synthesized by reversible addition–fragmentation chain transfer and atom transfer radical polymerization, was employed to prepare PDLCs with graft copolymer matrix in our previous work. Compared with linear copolymer matrix PDLCs prepared using a linear macroinitiator, it was found that, although low‐memory‐effect PDLCs were obtained, the driving voltage and transmittance of the PDLCs were unfortunately sacrificed to some extent. Thus, it is necessary to improve the electro‐optical properties of PDLCs on the basis of the original research performed by us. In the work reported in this article, a kind of linear macroinitiator with high refractive index and another graft macroinitiator with flexible branched chains were employed to prepare PDLCs. The results showed that by using mixed macroinitiators, the electro‐optical properties of PDLCs could be improved, and a possible mechanism is proposed.     

Preparation of polymer‐dispersed liquid crystal films containing a small amount of liquid crystalline polymer and their properties

Polymer‐dispersed liquid crystal (PDLC) films were synthesized by the copolymerization of liquid crystalline polymer (LCP) precursor, urethane acrylate (UA), and mesogenic monomer (AI) at different conditions. The morphology of polymer matrix changed with the weight ratio of polymer/liquid crystal (LC) ratio and curing temperature, resulting in a large change in the droplet size of LC domains in the PDLC film. The components used in the synthesis of polymer matrix, that is, the weight ratio of LCP, AI, and UA, also strongly influenced the morphology of PDLC films. A small amount of LCP was copolymerized with UA and AI in the preparation of polymer matrix to improve the electrooptical properties such as the viewing angle. Added LCP also affected the morphology and the properties of PDLC. The hydrophobicity of LCP caused changes in the droplet size of LC domain in PDLC films and the anchoring energy between matrix polymer and LC droplets. As the hydrophobicity of the matrix increases, the droplet size of LC domain also increases; on the contrary, anchoring energy decreased, leading to the decrease of driving voltage. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3178–3188, 2000     

An investigation into the morphology and electro‐optical properties of 2‐hydroxy ethyl methacrylate polymer dispersed liquid crystals

Polymer dispersed liquid crystal (PDLC) films are fabricated using E7 liquid crystals, tetraethylene glycol diacrylate (TeGDA) crosslinking agent, and 0–66.49 mol % 2‐hydroxy ethyl methacrylate (HEMA). The effects of different levels of HEMA addition on the microstructure and electro‐optical properties of the PDLC samples are examined using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, and UV‐Vis spectroscopy, respectively. The results show that the refractive index of the PDLC films is insensitive to the level of HEMA addition. However, an increasing HEMA content improves the degree of phase separation during the polymerization process and increases the size and uniformity of the liquid crystal domain. As a result, the electro‐optical properties of the PDLC films are significantly improved as the level of HEMA addition is increased. Overall, the results show that a PDLC comprising 40 wt % E7 liquid crystals, 33.51 mol % TeGDA and 66.49 mol % HEMA has a high contrast ratio (13 : 1) and a low driving voltage (10 V) and is therefore an ideal candidate for a wide variety of intelligent photoelectric applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of a chiral dopant on the electro‐optical properties of polymer‐dispersed liquid‐crystal films

Polymer‐dispersed liquid crystal (PDLC) films were prepared by the ultraviolet‐light‐induced polymerization of photopolymerizable monomers in nematic liquid crystal/monomer/chiral dopant composites, and the effect of the chiral dopant on the electro‐optical properties of the PDLC films was studied. It was demonstrated that the addition of a small amount of the chiral dopant increased the driving voltage somewhat but decreased the turn‐off time significantly. Furthermore, the transmittance of ultraviolet, visible, and near‐infrared light of the off state of PDLC films showing light scattering increased with increasing content of the chiral dopant, and the optimum electro‐optical properties of the PDLC films were obtained when the content of the chiral dopant was not more than 2 wt %. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Optimization of LC droplet size and electro‐optical properties of acrylate‐based polymer‐dispersed liquid crystal by controlling photocure rate

We investigated the effects of the different content ratios of 2‐ethylhexylacrylate (2‐EHA) and 2‐ethylhexylmethacrylate (2‐EHMA) on the relationships among the photopolymerization rate, morphology of liquid crystals (LCs) droplets, and electro‐optical properties of trifunctional urethane acrylate‐based polymer‐dispersed liquid crystal (PDLC) systems. Photo‐differential scanning calorimetry (DSC) analysis and resistivity measurement revealed that increasing 2‐EHMA content gradually decreased the photocure rate of trifunctional urethane acrylate‐based PDLCs, which prolonged the phase separation between the LC molecules and the prepolymers. Morphological observations and electro‐optical measurements demonstrated that trifunctional urethane acrylate‐based PDLCs with the 2‐EHA:2‐EHMA ratios from 4:1 to 3:2 in weight percent formed the favorable microstructures of LC droplets being within the range of 1–5 µm to scatter light efficiently and showed the satisfactory off‐state opacity and on‐state transmittance and the relatively low‐driving voltage. The microstructures of LC droplets and electro‐optical properties of trifunctional urethane acrylate‐based PDLCs could be usefully optimized by controlling the photocure rate using the different 2‐EHA/2‐EHMA content ratios. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3098–3104, 2013     

Preparation of a new polymer‐dispersed liquid crystal film by using phthalocyanine‐functional photocurable copolymer

A new, asymmetrical zinc phthalocyanine (aZnPc)‐functional photocurable copolymer was prepared by the combination of atom transfer radical polymerization and copper (I)‐catalyzed azide‐alkyne cyclo‐addition (CuAAC) click reaction and used as polymer matrix of polymer dispersed liquid crystal (PDLC) film. For this purpose, aZnPc was prepared through statistical condensation of 4‐tert‐butylphthalonitrile and 4‐pent‐4‐ynyloxyphthalonitrile. Double CuAAC click reaction between azido‐functional poly(methyl methacrylate‐co‐2‐(2‐bromoisobutyryloxy)‐ethyl methacrylate), terminal alkynyl‐substituted aZnPc, and 4‐ethynyl‐N,N‐dimethyl aniline yielded photocurable aZnPc‐functional copolymer. Thereby, synthesized copolymer was crosslinked in the presence of liquid crystalline mesogen 4′‐(octyloxy)‐4‐biphenylcarbonitrile by ultraviolet irradiation using benzophenone as initiator and ethylene glycol dimethacrylate as difunctional crosslinker. Thermal and optical properties of PDLC film were investigated by using differential scanning calorimetry and polarized optical microscopy. Smectic A liquid crystal mesophases were observed in both PDLC film and its mesogenic component 4′‐(octyloxy)‐4‐biphenylcarbonitrile. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41574.     

Electro‐optical properties of polymer‐dispersed liquid crystal prepared by controlled graft living radical polymerization

Living graft macromolecule has been prepared through reversible addition‐fragmentation chain transfer (RAFT) living radical polymerization in one step. Then, it was used to make polymer‐dispersed liquid crystal (PDLC) by controlling the mole ratio of styrene (St) to 1,6‐hexanediol diacrylate (HDDA) and adjusting the content of prepared graft macromolecule. The results showed that electro‐optical properties of PDLC have been optimized. Different concentration of living graft macromolecule and different mole ratio of St/HDDA led to substantial improvement of driving voltage (threshold voltage and saturation voltage) and memory effect of PDLC simultaneously. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

PEGylated hollow pH‐responsive polymeric nanocapsules for controlled drug delivery

Novel pH‐responsive PEGylated hollow nanocapsules (HNCaps) were fabricated through a combination of distillation–precipitation copolymerization and surface thiol–ene ‘click’ grafting reaction. For this purpose, SiO₂ nanoparticles were synthesized using the Stöber approach, and then modified using 3‐(trimethoxysilyl)propyl methacrylate (MPS). Afterward, a mixture of triethyleneglycol dimethacrylate (as crosslinker), acrylic acid (AA; as pH‐responsive monomer) and MPS‐modified SiO₂ nanoparticles (as sacrificial template) was copolymerized using the distillation–precipitation approach to afford SiO₂@PAA core–shell nanoparticles. The SiO₂ core was etched from SiO₂@PAA using HF solution, and the obtained PAA HNCaps were grafted with a thiol‐end‐capped poly(ethylene glycol) (PEG) through a thiol–ene ‘click’ reaction to produce PAA‐g‐PEG HNCaps. The fabricated HNCaps were loaded with doxorubicin hydrochloride (DOX) as a model anticancer drug, and their drug loading and encapsulation efficiencies as well as pH‐dependent drug release behavior were investigated. The anticancer activity of the drug‐loaded HNCaps was extensively evaluated using MTT assay against human breast cancer cells (MCF7). The cytotoxicity assay results as well as superior physicochemical and biological features of the fabricated HNCaps mean that the developed DOX‐loaded HNCaps have excellent potential for cancer chemotherapy. © 2020 Society of Chemical Industry     

Optical switching behavior of polymer‐dispersed liquid crystal composite films with various novel azobenzene derivatives

Polymer‐dispersed liquid crystal (PDLC) composite films were fabricated by thermal polymerization with E7 liquid crystal, monomers, and novel azobenzene derivatives synthesized in this study. To investigate the effects of azocompounds on the optical switching of PDLC films, a series of novel azobenzene derivatives of 4‐alkyloxy‐4′‐methoxyazobenzene with carbon numbers of 3–6, chiral compounds of amyl‐4‐(4‐hexyloxyphenylazo)benzoate, and bornyl‐4‐(4‐hexyloxyphenylazo)benzoate were synthesized. The compounds synthesized in this investigation were identified using FTIR, NMR, and elemental analysis. The optical texture of the composite films was analyzed under crossed nicols with a polarizing microscope. The morphological observation of the solid polymer in the composite films was performed with a scanning electron microscope (SEM). The optical behavior of the composite films on UV irradiation and the effects of the curing time on the thermal stability of the composite films were investigated. Isomerization of the azobenzene derivatives due to UV irradiation was confirmed by a texture study and image recording method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 789–799, 2004     

Effect of graft copolymer matrix prepared by reversible addition–fragmentation chain transfer and atom transfer radical polymerization on the electro‐optical properties of polymer‐dispersed liquid crystals

A type of graft macroinitiator, synthesized by reversible addition–fragmentation chain transfer (RAFT) and atom transfer radical polymerization, was employed to prepare polymer‐dispersed liquid crystals (PDLCs) with graft copolymer matrix; meanwhile, a linear macroinitiator was also synthesized via RAFT polymerization. The effect of linear and graft macroinitiators on the electro‐optical (EO) properties of the PDLCs was investigated. The results showed that the graft macroinitiator could make a large difference to the EO properties of the PDLCs. The memory effect was reduced remarkably, but the driving voltage increased and transmittance decreased. A possible mechanism is presented. © 2014 Society of Chemical Industry     

Enhancement of electro‐optical properties in holographic polymer‐dispersed liquid crystal films by incorporation of multiwalled carbon nanotubes into a polyurethane acrylate matrix

Holographic polymer‐dispersed liquid crystal (HPDLC) films were fabricated with varying amounts of multiwalled carbon nanotubes (MWCNTs) to optimize the electro‐optical performance of the HPDLC films. The MWCNTs were well dispersed in the prepolymer mixture up to 0.5 wt%, implying that polyurethane acrylate (PUA) oligomer chains wrap the MWCNTs along their length, resulting in high diffraction efficiency and good phase separation. The hardness and elastic modulus of the polymer matrix were enhanced with increasing amounts of MWCNTs because of the reinforcement effect of the MWCNTs with intrinsically good mechanical properties. The increased elasticity of the PUA matrix and the immiscibility between the matrix and the liquid crystals (LCs) gradually increased the diffraction efficiency of the HPDLC films. However, the diffraction efficiency of HPDLC films with more than 0.05 wt% MWCNTs was reduced, caused by poor phase separation between the matrix and LCs because of the high viscosity of the reactive mixture. HPDLC films showing a low driving voltage (<3 V µm^?1), a fast response time (<10 ms) and a high diffraction efficiency (>75%) could be obtained with 0.05 wt% MWCNTs at 40 wt% LCs. Copyright © 2010 Society of Chemical Industry     

Optical property enhancement of dye‐PDLC using active reflector structure

The enhancement of electro‐optical properties in reflective‐type dye polymer dispersed liquid crystal (PDLC) has been achieved by applying an additional white PDLC layer along with dye PDLC layer. This newly modified structure that consists of white PDLC layer and scattering reflector acts as an active reflector. In this practice, an additional arrangement of a polymer barrier layer is made‐up over white PDLC layer, to block the absorption of any solution from dye PDLC. The contrast ratio of this new configuration is almost doubled with low driving voltage and high ON reflectance. Simultaneously, the “off” state has been observed darker than single layer dye PDLC structure. This new configuration can be potentially significant for various display applications such as E‐paper, outdoor billboard, and flexible display. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and electrooptic study of reverse mode polymer dispersed liquid crystal: Performance augmentation with the doping of nanoparticles and dichroic dye

Reported herein, the preparation, morphological, and electrooptic (EO) characterization of reverse mode polymer dispersed liquid crystals (PDLCs) with nematic liquid crystal (LC) and UV curable polymer optical adhesive using polymerization induced phase separation method. The PDLCs are switchable between transparent and opaque states due to the homeotropic and planar alignment of LC in their OFF and ON states of applied voltage, respectively. Further, effect of doping of a fixed concentration of azo dye and silica nanoparticles (NPs) on morphological, EO and response characteristics of same PDLC sample was also analyzed. Experimental results showed that doped reverse mode PDLCs have the higher OFF state optical transmission and boost up in the scattering ON state compared with pristine reverse mode PDLC. The phenomenon is also supported by extinction coefficient and absorption study based on Beer's law. The threshold and operating voltages were found reduced ~1.56 and ~1.73 times for NPs and (NPs + dye) doped reverse mode PDLCs, respectively, along with better contrasts to the pristine reverse mode PDLC. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48745.     

Electro‐optical properties of polymer dispersed liquid crystal prepared by successively controlled living radical polymerization

Polymer dispersed liquid crystal (PDLC) films were obtained by successive controlled living radical polymerizations: starting polystyrene (M1) was obtained by reversible addition‐fragmentation polymerization (RAFT), M1 was converted to P‐chloromethylated polystyrene (M2) which was grafted with polystyrene branches by atom transfer radical polymerization (ATRP) to yield RAFT‐initiating graft polymer containing trithiocarbonate moieties in the backbone (M3, RAFT‐active grafted polystyrene), and then PDLC films were prepared by photo‐induced RAFT copolymerization of methyl acrylate with M3 in the presence of a nematic liquid crystal. The electro‐optical properties of the films were investigated for the purpose to apply them to optical devices. Experimental results showed that preferable properties could be acquired by controlling the amount of M3 and the liquid crystal E7 in the polymer matrix of PDLC films. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

The kinetics and morphology of polymer dispersed liquid crystals by doped crylic acid

It is widely appreciated that electro‐optical activity in polymer dispersed liquid crystals (PDLCs) depends on phase separation of polymer and liquid crystals (LCs). The morphology of the LCs domains depends on the detail of the chemical and physical processes active during the formation of domains. This work discusses two‐phase morphology in an acrylate‐based system that developed during polymerization induced phase separation. UV/VIS spectrometer is used for monitoring the polymerization of the PDLCs by real‐time scattering. The doped crylic acid accelerated the speed of polymerization. The electro‐optical properties of PDLCs films are measured by Polarimeter (PerkinElmer Model 341). The lower threshold voltage was obtained by doped crylic acid at suitable ratio. The polarizing optical microscopy and Fourier transform infrared image system are used for depicting the morphology of LC droplets in polymer matrix. The sizes and dispersion of LC droplets were influenced by doped crylic acid which accelerated the speed of polymerization. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Comparative study on the electrooptical properties of polymer‐dispersed liquid crystal films with different mixtures of monomers and liquid crystals

This article deals with the study of polymer‐dispersed liquid crystal (PDLC) films that consisted of microdroplets of liquid crystals (LCs) dispersed in a polymer matrix. The PDLC films were fabricated by the photoinduced phase separation method under room‐temperature conditions. To determine the extent of the effects of the molecular structures and their physical properties of different mixtures of monomers and LCs on the morphology and electrooptical properties of the PDLC films, various mixtures were used. A detailed discussion of the obtained results is given. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and characterization of hybrid thiol‐ene/epoxy UV–thermal dual‐cured systems

Hybrid thiol‐ene/epoxy coatings were prepared by combining thiol‐ene photo‐curable formulations with epoxy monomers, through a dual UV–thermal curing process. An increase in glass transition temperature and in storage modulus was observed for the hybrid thiol‐ene/epoxy coatings when compared with the pristine thiol‐ene UV‐cured system. Also, the bisphenol A moieties introduced into the hybrid networks during the dual‐curing process induced an increase in thermal stability of the cured materials. It has been demonstrated that the addition of epoxy monomer to the thiol‐ene photo‐curable system is a good strategy to follow in order to improve the final properties of thiol‐ene‐based coatings leading to a wide range of possible applications for the hybrid materials. Copyright © 2010 Society of Chemical Industry     

The effect of photoinitiator concentration and structures of RAFT macroinitiators on the memory effect of polymer dispersed liquid crystals

The article aimed to decrease the memory effect of polymer dispersed liquid crystals (PDLCs) films, reversible additional‐fragmental chain transfer (RAFT) polymerization was used to synthesize RAFT‐polystyrene (RAFT‐PS), which was a kind of RAFT macroinitiators and used to prepare PDLCs via photo polymerization induced phase separation (PIPS). Different RAFT agents were used to synthesize RAFT‐PS. The effect of photoinitiator concentration on the memory effect of these PDLCs was investigated, and the effect of structures of RAFT macroinitiators on the memory effect of the PDLCs was also discussed. The results showed that PDLC films with higher photoinitiator concentration and polymer matrix which had two rigid chains in two ends showed lower memory effect, which could be reduced from 10.9% to 2.5% in this experiment. POLYM. ENG. SCI., 55:8–13, 2015. © 2014 Society of Plastics Engineers     

Thiol‐ene photofunctionalization of 1,4‐polymyrcene

1,4‐Polymyrcene was synthesized by anionic polymerization of β‐myrcene and was subjected to photochemical functionalization with various thiols (i.e. methyl thioglycolate, methyl 3‐mercaptopropionate, butyl 3‐mercaptopropionate, ethyl 2‐mercaptopropionate and 2‐methyl‐2‐propanethiol) using benzophenone/UV light as the radical source. The yield of thiol addition to the trisubstituted double bonds of 1,4‐polymyrcene decreased in the order 1° thiol (ca 95%) > 2° thiol (ca 80%) > 3° thiol (<5%), due to the reversibility of the thiol‐ene reaction. Remarkably, thiol addition to the side‐chain double bonds was 8 ? 10 times (1° thiol) or 24 times (2° thiol) faster than to the main‐chain double bonds, which can be explained by the different accessibility of the double bonds and steric hindrance. Despite the use of a 10‐fold excess of thiol with respect to myrcene units, the thiol‐ene addition was accompanied by chain coupling reactions, which in the extreme case of 3° thiol (or in the absence of thiol) resulted in the formation of insoluble crosslinked material. As an example, a methyl‐thioglycolate‐functionalized 1,4‐polymyrcene was saponified/crosslinked to give submicron polyelectrolyte particles in dilute alkaline solution. © 2018 Society of Chemical Industry