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.     

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     

Reversible addition–fragmentation chain transfer polymerization of styrene with benzoimidazole dithiocarbamate as a reversible addition–fragmentation chain transfer agent

Two novel dithiocarbamates [2‐Y‐benzoimidazole‐1‐carbodithioic acid benzyl esters: Y = methyl (1b) or phenyl (1c)] were synthesized and successfully used in the reversible addition–fragmentation chain transfer (RAFT) polymerization of styrene in bulk with thermal initiation. The effects of the temperatures and concentration ratios of the styrene and RAFT agents on the polymerization were investigated. The results showed that the polymerization of styrene could be well controlled in the presence of 1b or 1c. The linear relationships between ln([M]₀/[M]) and the polymerization time (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) indicated that the polymerizations were first‐order reactions with respect to the monomer concentration. The molecular weights increased linearly with the monomer conversion and were close to the theoretical values. The molecular weight distributions [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] were very narrow from 5.3% conversion up to 94% conversion (M_w/M_n < 1.3). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 560–564, 2006     

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     

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     

Holographic polymer‐dispersed liquid crystals using vinyloxytrimethylsilane

BACKGROUND: To reduce the driving voltage of transmission holographic polymer‐dispersed liquid crystals (HPDLCs), the polymer interface was modified by incorporating various amounts of vinyloxytrimethylsilane (VOTMS) monomer to the conventional grating formulation based on polyurethane acrylate (PUA). RESULTS: With the addition of increasing amounts of VOTMS, the contact angle of the film and the droplet size of the liquid crystal (LC) monotonically increased, implying that the VOTMS segments of the polymer are preferentially exposed to the interfaces and provide greater immiscibility with LC molecules. The operating voltage monotonically decreased with increasing VOTMS content with a minimum switching voltage of about 15 V with a response time of about 10 ms. However, in the presence of VOTMS, the droplets coalesced and caused random scattering, thus lowering the off‐state diffraction efficiency below that of virgin PUA. CONCLUSION: It was found that VOTMS was essential to drive the film. The VOTMS segments of the polymer are preferentially exposed to the polymer/LC interfaces and decrease the surface anchoring strength and also influence the orientation of LC droplets. Also, lower molecular weight bifunctional polypropylene glycol generally gave greater diffraction efficiency, confirming that grating formation is favoured with higher crosslink density due to the greater polymer/LC phase separation. Copyright © 2008 Society of Chemical Industry     

Reversible addition–fragmentation chain transfer polymerization of styrene using a novel thiophene dithioester as the reversible addition–fragmentation chain transfer agent

Benzyl thiophene‐2‐carbodithioate and 2‐methyl‐2‐(4‐methylcyclohex‐3‐enyl)propyl thiophene‐2‐carbodithioatewere synthesized. The reversible addition–fragmentation chain transfer polymerizations of styrene with benzyl thiophene‐2‐carbodithioate and 2‐methyl‐2‐(4‐methylcyclohex‐3‐enyl)propyl thiophene‐2‐carbodithioate as chain‐transfer agents and with 2,2′‐azobisisobutyronitrile as an initiator were carried out. The polymerization kinetics were investigated. An ab initio calculation method was used to explore the differences between benzyl thiophene‐2‐carbodithioate and benzyl benzodithioate. The structure of the obtained polymers was characterized with ¹H‐NMR. Chain‐extension experiments of the obtained polymer with styrene were carried out. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis of 1,3‐benzodioxole end‐functionalized polymers via reversible addition–fragmentation chain transfer polymerization

Reversible addition–fragmentation chain transfer (RAFT) polymerization of styrene was carried out in the presence of a novel RAFT reagent, bearing 1,3‐benzodioxole group, benzo [1,3]dioxole‐5‐carbodithioic acid benzo [1,3]dioxol‐5‐ylmethyl ester (BDCB), to prepare end‐functionalized polystyrene. The polymerization results showed that RAFT polymerization of styrene could be well controlled. Number–average molecular weight (M_n(GPC)) increased linearly with monomer conversion, and molecular weight distributions were narrow (M_w/M_n < 1.4). The successful reaction of chain extension and analysis of ¹H NMR spectra confirmed the existence of the functional 1,3‐benzodioxole group at the chain‐end of polystyrene. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3535–3539, 2006     

Improved dispersibility of multi‐wall carbon nanotubes with reversible addition–fragmentation chain transfer polymer modification

A non‐covalent approach is used to modify multi‐wall carbon nanotubes (MWCNTs) via a block polymer that can be synthesized in aqueous solvent through reversible addition–fragmentation chain transfer polymerization. The block polymer consists of oligo(ethylene glycol) methyl ether acrylate and acrylic acid. The hydrophobic backbone is significantly adsorbed on hydrophobic MWCNT surfaces, which is verified using transmission electron microscopy, thermogravimetric analysis and X‐ray photoelectron spectroscopy. The coated block polymer can prevent the aggregation of MWCNTs and improve their dispersibility in water. The MWCNTs after modification are stable in water even after standing in a long‐term test. © 2015 Society of Chemical Industry     

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     

Modeling analysis of chain transfer in reversible addition‐fragmentation chain transfer polymerization

The validity of simplifying the reversible addition‐fragmentation chain transfer (RAFT) polymerization as a degenerative chain transfer process was verified in this work. The simplified chain transfer mechanism enabled the direct modeling investigation of chain transfer coefficient in the RAFT polymerization. It also gave the analytical expressions for concentration, chain length, and polydispersity of various chain species. The comparison between the simulations based on chain transfer mechanism and those from general RAFT mechanism showed that this simplified mechanism can accurately predict RAFT polymerization in the absence of side reactions to adduct radicals other than fragmentation. However, significant errors are introduced at high conversion when side reactions to adduct are present. The chain transfer coefficient of RAFT agent is the key factor in RAFT polymerization. The polydispersity is more sensitive to chain transfer coefficient at low conversion. At high conversion, however, the polydispersity is mainly determined by termination, which can be controlled by RAFT agent concentration and the selection of initiator. At last, an analytical equation is derived to directly estimate chain transfer coefficient of RAFT agent from the experimental data. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

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     

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     

Nanoporous well‐defined reversible addition–fragmentation chain transfer polymer of N‐acrylamido‐l‐tryptophan: synthesis and characterization

A nanoporous polymer with a chiral pendant chain of N‐acrylamido‐l ‐tryptophan was synthesized through a reversible addition–fragmentation chain transfer polymerization process using a dithiobenzoate derivative as chain transfer agent. The polymerization exhibited the usual characteristics of living processes, though slow polymerization rate and low percentage conversion for a chain extension experiment were observed. Depending on the monomer/chain transfer agent ratio, poly(N‐acrylamido‐l ‐tryptophan) with number‐average molecular weights between 640 and 4340 g mol^?1 and molar mass dispersities between 1.10 and 1.24 was obtained, as evidenced from gel permeation chromatography. Scanning electron microscopy images indicated that the polymer was porous. Nitrogen adsorption analysis of the polymer evidenced the presence of mesopores (2–19 nm) associated with micropores (0.45–2 nm) according to the Barrett–Joyner–Halenda method with a specific Brunauer–Emmett–Teller surface area of 22.98 m² g^?1. © 2013 Society of Chemical Industry     

Poly(dimethylsiloxane‐b‐styrene) diblock copolymers prepared by reversible addition‐fragmentation chain transfer polymerization: Kinetic model

Well‐defined polydimethylsiloxane‐block‐polystyrene (PDMS‐b‐PS) diblock copolymers were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization using a functional PDMS‐macro RAFT agent. The RAFT polymerization kinetics was simulated by a mathematical model for the RAFT polymerization in a batch reactor based on the method of moments. The model described molecular weight, monomer conversion, and polydispersity index as a function of polymerization time. Good agreements in the polymerization kinetics were achieved for fitting the kinetic profiles with the developed model. In addition, the model was used to predict the effects of initiator concentration, chain transfer agent concentration, and monomer concentration on the RAFT polymerization kinetics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Holographic‐polymer‐dispersed liquid crystals doped with poly(vinyl carbazole)–fullerene

The effects of poly(vinyl carbazole) (PVK) doped to a poly(urethane acrylate) matrix in holographic‐polymer‐dispersed liquid crystals were studied. With the addition and increasing amounts of PVK, the driving voltage and rising time of the films decreased because of the increased effective local electric field across the liquid crystal (LC) droplet. Off‐state diffraction efficiency was increased with the addition and increasing amounts of PVK presumably because of the increased elasticity of the polymer matrix, which augmented the phase separation of the polymer and LC by effectively squeezing the LC molecules out of the polymer matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of monomer structure on the morphology of polymer network and the electro‐optical property of reverse‐mode polymer‐stabilized cholesteric texture

The morphologies of the polymer networks in the polymer network/LC composite of reverse‐mode polymer‐stabilized cholesteric texture (PSCT) films was observed. The polymer network/LC composite was prepared from photopolymerization of the acrylate monomers, which had rod‐like rigid cores in monomer/LC mixture. The effects of the structure of the acrylate monomers on the morphology of polymer network were studied. The acrylate monomer without flexible pacers between the acrylate functional groups and the rigid core formed rice‐grain‐like polymer network with poor orientation. The acrylate monomer with flexible pacers formed fiber‐like polymer network with better orientation. Meanwhile, the effects of morphology of polymer network on the electro‐optical property of reverse‐mode PSCT films were also investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Reversible addition‐fragmentation chain transfer (RAFT) polymerization of styrene using novel heterocycle‐containing chain transfer agents

BACKGROUND: Controlled/‘living’ radical polymerization is a new and robust method to synthesize polymers with predetermined molecular weight, narrow polydispersity and tailored architecture. Several methods have been developed but reversible addition‐fragmentation chain transfer (RAFT) has several advantages over the other methods. It has been reported that the effectiveness of RAFT agents depends strongly on the nature of the Z and R groups. RESULTS: Three new dithiocarbamates, namely (2‐ethoxy carbonyl)‐prop‐2‐yl‐pyrrole‐1‐carbodithioate (CTA‐A), (1‐phenyl ethyl)‐pyrazole‐1‐carbodithioate (CTA‐B) and (2‐ethoxy carbonyl)‐prop‐2‐yl‐pyrazole‐1‐carbodithioate (CTA‐C), were synthesized for studying the effect of the Z and R group of a chain transfer agent on the RAFT polymerization of styrene, initiated by 2,2′‐azobisisobutyronitrile. Well‐controlled molecular weight with narrow polydispersity (1.10–1.46) was achieved. The increase in molecular weight with conversion is linear and follows first‐order kinetics. CONCLUSION: The detailed kinetic results show that the structure of the activating (Z) group of dithiocarbamates has significant effects on the reactivity of dithiocarbamates towards the polymerization of styrene. In the homopolymerization of styrene it was found that, from the polydispersity index of polystyrenes obtained and the kinetic results, the pyrazole‐based dithiocarbamates (CTA‐B and CTA‐C) are very effective compared to the pyrrole‐based dithiocarbamate (CTA‐A). All the polymerizations show controlled living characters. Copyright © 2007 Society of Chemical Industry     

End‐functional polymers,thiocarbonylthio group removal/transformation and reversible addition–fragmentation–chain transfer (RAFT) polymerization

This review focuses on processes for thiocarbonylthio group removal/transformation of polymers synthesized by radical polymerization with reversible addition‐fragmentation‐chain transfer (RAFT). A variety of processes have now been reported in this context. These include reactions with nucleophiles, radical‐induced reactions, thermolysis, electrocyclic reactions and ‘click’ processes. We also consider the use of RAFT‐synthesized polymers in the construction of block or graft copolymers, functional nanoparticles and biopolymer conjugates where transformation of the thiocarbonylthio group is an integral part of the process. This includes the use of RAFT‐synthesized polymers in other forms of radical polymerization such as atom transfer radical polymerization or nitroxide‐mediated polymerization, and the ‘switching’ of thiocarbonylthio groups to enable control over polymerization of a wider range of monomers in the RAFT process. With each process we provide information on the scope and, where known, indicate the mechanism, advantages and limitations. Copyright © 2011 Society of Chemical Industry     

Star graft copolymer via grafting‐onto strategy using a comb!ination of reversible addition–fragmentation chain transfer arm‐first technique and aldehyde–aminooxy click reaction

A facile synthetic pathway to a multi‐arm star graft polymer has been developed via a grafting‐onto strategy using a combination of a reversible addition–fragmentation chain transfer (RAFT) arm‐first technique and aldehyde–aminooxy click reaction. A star backbone bearing aldehyde groups was prepared by the RAFT copolymerization of acrolein (Ac), an existing commercial aldehyde‐bearing monomer, with styrene (St), followed by crosslinking of the resultant poly(St‐co‐Ac) macro‐RAFT agent using divinylbenzene. The aldehyde groups on the star backbone were then used as clickable sites to attach poly(ethylene glycol) (PEG) side chains via the click reaction between the aldehyde groups and aminooxy‐terminated PEG, leading to a structurally well‐defined star graft copolymer with arms consisting of poly(St‐co‐Ac) as backbone and PEG as side chains. Crystalline morphology and self‐assembly in water of the obtained star graft copolymer were also investigated. Opportunities are open for the star graft copolymer to form either multimolecular micelles or unimolecular micelles via control of the number of grafted PEG side chains. © 2013 Society of Chemical Industry