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     

Electrically and thermally modulated optical properties of polymer dispersed chiral liquid crystal

The polymer dispersed chiral liquid crystals (PDCLCs) film was fabricated by photopolymerization induced phase separation (PIPS) of chiral liquid crystal (CLC)/polymerizable monomers/photoinitiator composites. The effects of the electrical and thermal modulation on optical rotation properties of PDCLCs film were investigated. The microsized liquid crystal droplets were resulted from the rapid polymerization of trifunctional monomers. The effects of the electrically and thermally modulated on realignment of liquid crystal director were investigated. It was found that the intensity of electric and thermal field influenced the alignment of liquid crystal droplets' director on PDCLCs film, and the electro‐optical properties of the composites were affected accordingly. The principle of free energy minimum was used for explaining the change of optical rotation and transmittance of PDCLCs film with applying the voltage to the film. The dispersion and sizes of liquid crystal droplets were described by polarizing optical microscope (POM). POLYM. COMPOS., 31:1535–1540, 2010. © 2009 Society of Plastics Engineers     

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     

Molecularly imprinted polymer nanomaterials and nanocomposites by controlled/living radical polymerization

Since the pioneering work of Wulff and Mosbach more than 30 years ago, molecular imprinting of synthetic polymers has emerged as a robust and convenient way for synthesizing polymeric receptor materials bearing specific recognition sites for target molecules. The resulting materials, molecularly imprinted polymers (MIPs), are therefore commonly referred to as ‘plastic antibodies’. They are obtained by polymerizing a scaffold around a target, or a derivate thereof, which acts as a molecular template. MIPs have been successfully applied in many areas including affinity separation, immunoassays, chemical sensing, solid-phase extraction, drug delivery, cell and tissue imaging, direct synthesis and catalysis. In terms of affinity and selectivity, MIPs are on a par with biological receptors like antibodies, and this is accompanied by a superior chemical and physical stability, compatibility with organic media, reusability, easy engineering and low cost. These advantages represent the main reasons for the wide interest raised around molecularly imprinted materials. Mainly produced by free radical polymerization (FRP) of vinyl monomers, MIPs have also taken advantage of the introduction of controlled/living radical polymerization (CRP) techniques, which have literally transformed polymer chemistry over the last decade. This review describes the advantages arising from the use of CRP in synthesizing MIPs, both in terms of sheer binding properties as well as for their remarkable potential for post-polymerization functionalization, for the synthesis of MIP nanomaterials and for the integration of MIPs into composites and hybrid materials. The benefits of using CRP are critically assessed with respect to the still largely applied FRP and guidelines are provided for choosing the most convenient technique to fit a specific targeted application of MIPs.     

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     

Enhancing molecularly imprinted polymer binding properties via controlled/living radical polymerization and reaction analysis

Fractional double bond conversion and associated template binding parameters of molecularly imprinted polymers were explored in this study in relation to initiator type and concentration, crosslinking monomer length, temperature, and solvent concentration. Controlled/living polymerization techniques were used to synthesize recognitive poly(methacrylic acid-co-ethylene glycol dimethacrylate) (poly(MAA-co-EGDMA)) networks which resulted in a 63% increase in the number of binding sites at approximately equivalent average binding affinity while retaining selectivity of the target molecule, ethyladenine-9-acetate. This is hypothesized to be attributed to a decrease in kinetic chain length and/or a more narrow dispersity of kinetic chains which leads to increased structural homogeneity and increased stability and integrity of binding sites. Reaction analysis of a typical poly(MAA-co-EGDMA) molecularly imprinted network measured via differential scanning calorimetry revealed low double bond conversion (35 ± 2.3% at 0 °C to 54 ± 1.9% at 50 °C) which is due to severely constrained network formation; therefore, the final composition of imprinted polymers does not represent the initial formulation when using significant amounts of short bifunctional crosslinking monomer. Optimization of conventional photoinitiator was shown to lead to a small improvement in template selectivity at equivalent affinity and capacity. However, the use of controlled/living polymerization techniques within the field of imprinted polymers has the greatest potential to improve the structural homogeneity and drastically enhance the binding parameters. Polymerization reaction analysis and the use of controlled polymerization strategies will lead to a greater understanding of the imprinting mechanism, optimization of binding parameters, and an increase in the application potential of imprinted networks.     

液晶聚合物调控的蓄热调温材料的储热性能

通过3,3′,4,4′-二苯甲酮四甲酸二酐(BPTCD)与聚乙二醇2000(PEG2000)的酯化反应,制备了具有光热响应的相变聚合物BPTCD-PEG,该聚合物在相变过程中可以形成液晶态.在偏光显微镜下,BPTCD-PEG呈典型的焦锥花形向列相液晶织构.采用DSC对BPTCD-PEG的热性能进行表征,结果表明,BPT...     

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     

Polymer-dispersed liquid crystal materials prepared by electron-beam-initiated polymerization

Polymer-dispersed liquid crystal (PDLC) films were prepared using electron beam radiation by a polymerization-induced phase separation process. The composite material was obtained from a blend including a polyester acrylate and the nematic liquid crystal mixture E7. The electro-optic properties of the PDLC films were investigated as a function of film thickness. The obtained transmission vs. voltage curves exhibit a good reproducibility, low threshold voltages, and a high transmission in the on state. © 1995 John Wiley & Sons, Inc.     

Solution self‐assembly of tailor‐made macromolecular building blocks prepared by controlled radical polymerization techniques

This review describes the preparation of colloidal aggregates (spherical micelles, cylindrical micelles, polymer vesicles, multicompartment micelles, polyion complexes, schizophrenic micelles) using bottom‐up self‐assembly approaches. In particular, it focuses primarily on the self‐organization of well‐defined macromolecular building blocks (macrosurfactants, polysoaps, polyelectrolytes) synthesized by controlled radical polymerization techniques such as atom transfer radical polymerization, reversible addition fragmentation transfer polymerization and nitroxide‐mediated polymerization. The goal of this review is to highlight that these versatile techniques of polymer synthesis allow the preparation of unprecedented nanostructures in dilute solutions. Copyright © 2006 Society of Chemical Industry     

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     

Mechanical properties of cross-linked polymer particles prepared by nitroxide-mediated radical polymerization in aqueous micro-suspension

The compressive strengths of micron-sized, cross-linked poly(styrene-divinylbenzene) particles synthesized by conventional radical copolymerization (70 °C) and nitroxide (TEMPO)-mediated radical copolymerization (125 °C) in aqueous micro-suspension have been measured. In the conventional system, the breaking energies and the compressive strengths of the particles (after removal of unreacted monomer) remained approximately constant from low to high conversion, whereas in the NMP system, both quantities increased close to linearly with conversion. The results suggest that the network formation is more homogeneous in the NMP system than in the conventional system.     

Molecular engineering of liquid crystal polymers by living polymerization

Summary This paper describes the synthesis of poly{11-[(4-cyano-4-biphenyl)oxy]undecanyl vinyl ether-co-2-[(4-cyano-4-biphenyl)oxy]ethyl vinyl ether} A/B {poly[(6-11)-co-(6-2)]A/B} where A/B refers to the molar ratio between the monomers 6-11 and 6-2, with number average molecular weights above 15, by living cationic polymerization. The phase behavior of the resulting copolymers was discussed as a function of copolymer composition. Within this range of molecular weights, in the first heating scan poly(6-11) exhibits a melting and an enantiotropic s_A phase, while poly(6-2) an inverse s_C phase. In the second and subsequent heating scans poly(6-11) displays an enantiotropic s_X (unidentified smectic phase) and a s_A mesophase, while poly(6-2) only a glass transition temperature. Depending on composition, poly[(6-11-co-6-2)]A/B either display an enantiotropic nematic, enantiotropic s_A or both enantiotropic nematic and anantiotropic s_A phases.     

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.     

Electro-optical properties of the normally transparent type anisotropic polymer dispersed liquid crystal films

We fabricate normally transparent type of polymer dispersed liquid crystal (PDLC) films, which are composed of nematic liquid crystals in anisotropic polymer network. The glass substrates of the films are treated with rubbing such that the polymer and liquid crystal molecules are plane parallel aligned in the sample cell. The liquid crystals used are 5CB and 7CB. The polymer is cured at a variety of UV wavelengths and intensities. The electro-optical properties of these PDLC films are reported. This type of transparent PDLC shows an improvement in the transparency of the clear state and a decrease in the driving voltage.     

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     

Lithographic results of electron beam photoresists prepared by living free radical polymerization

Summary A new family of random copolymers composed of chloromethylstyrene and a silicon based styrenic monomer was prepared using living radical polymerization. The lithographic efficiency of the resulting electron beam resists was examined. A pronounced improvement on the lithographic resolution and image quality of resists with a narrow molecular mass distribution was observed and is described. Received: 20 April 1999/Revised version: 11 June 1999/Accepted: 17 June 1999     

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     

Benzotriazinyl‐mediated controlled radical polymerization of styrene

The stable free radical polymerization (SFRP) process based on (1,3‐diphenyl‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl), the so‐called ‘Blatter radical’, and several C‐7 substituted derivatives is introduced for the first time for the polymerization of styrene. Polystyrenes characterized by polydispersity indices in the 1.05 ? 1.27 range were obtained in the presence of the Blatter radical and its derivatives containing CF₃, Ph, Fur‐2‐yl and 4‐PhC₆H₄ substituents, while polymerization proceeded either in a non‐controlled manner or in very low polymerization yields in the presence of derivatives containing halogen (Cl, Br, I) substituents. This preliminary investigation, demonstrating the potential use of the Blatter radical and its derivatives in mediated SFRP, creates new opportunities to design and develop radicals to optimize performance in such polymerization processes. © 2013 Society of Chemical Industry     

Electro–optic studies on polymer‐dispersed liquid crystal composite films. I. Composites of PVB–E7

The electro‐optic performance characteristic of polymer‐dispersed liquid crystal (PDLC) composite films out of poly(vinyl butyral) (PVB) and nematic liquid crystal (E7) have been studied for a wide range of PVB–E7 composite compositions (20–70 wt % of E7). Composites were prepared by solvent casting from chloroform at room temperature. A scanning electron microscopy study showed that a E7 phase is continuously embedded in chink‐like structure of PVB matrix. Optical transmittance of the composite films (of 60 and 70 wt % loading of E7) under an alternating current (ac) electric field (0–250, V_p‐p) and frequency (50 Hz to 1 KHz) were measured employing He Ne laser (λ = 632.8 nm). The results indicate that the (PVB–E7) composite exhibits a memory effect. In the memory state, higher transmittance is preserved without applying voltage. The memory state can be erased and changed to the scattering Off‐state by heating the film to the clearing temperature of the liquid crystal. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3485–3491, 1999