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     

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.     

Macro reversible addition–fragmentation chain transfer agent mixture as a means to enhance the electro‐optical performance of polymer‐dispersed liquid crystals

Macro reversible addition–fragmentation chain transfer (RAFT) agents, i.e. RAFT polystyrene (RAFT‐PS) and RAFT poly(n‐butyl acrylate) (RAFT‐PBA), were mixed. Polymer‐dispersed liquid crystals (PDLCs) were prepared using the mixture together with methyl acrylate and liquid crystal E7. The electro‐optical properties of the PDLCs obtained were investigated. The results showed that the advantages of the electro‐optical properties of RAFT‐PS‐ and RAFT‐PBA‐dependent PDLCs could be combined in RAFT agent mixture‐dependent PDLCs. Copyright © 2011 Society of Chemical Industry     

Fabrication of polymer‐dispersed liquid crystals with low driving voltage based on the thiol‐ene click reaction

Polymer‐dispersed liquid crystals (PDLCs ) with a well‐defined polymer matrix were successfully fabricated by the thiol‐ene click reaction based on poly(ethylene glycol) diacrylate (PEGDA ) and trimethylolpropanetris‐(3‐mercaptopropionate) (TMTP ). UV ?visible spectrophotometry, Fourier transform IR spectroscopy, SEM and polarized optical microscopy were employed to explore the PDLC films obtained. Electro‐optical properties were studied with a UV ?visible spectrophotometer. It was found that the PDLC films with optimal thiol content fabricated by the thiol‐ene click reaction showed high transmittance, low driving voltage and a low memory effect. It was concluded that the driving voltage change of PDLCs with different thiol concentrations was caused by the polymerization rate and the structure of the polymer matrix. © 2017 Society of Chemical Industry     

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     

Optimization of the property profile of poly‐L‐lactide by synthesis of PLLA‐polystyrene–block copolymers

Diblock and triblock copolymers of poly‐L ‐lactide (PLLA) and polystyrene (PS) were synthesized and the mechanical properties of these copolymers studied. Free radical polymerization of styrene in the presence of 2‐mercaptoethanol as functional chain transfer agent produced mono‐functionalized PS‐blocks which were used as macroinitiators in the subsequent ring opening polymerization (ROP) of L ‐lactide to produce the diblock copolymers. Furthermore a α‐ω‐bishydroxyl functionalized PS‐block was synthesized by RAFT, which was then engaged as bifunctional initiator for the ROP of L ‐lactide to provide the triblock copolymers PLLA‐PS‐PLLA. Through the copolymerisation and high molar masses, it was possible to achieve an improved mechanical property profile, compared with pure PLLA, or the analogous blends of PLLA and PS. A weight fraction of PS of 10–30% was found to be the optimal range for improving the heat deflection temperature (HDT), as well as mechanical properties such as ultimate tensile strength or elongation at break. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

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     

Ab initio reversible addition–fragmentation chain transfer emulsion polymerization of styrene/butyl acrylate mediated by poly(acrylic acid)‐block‐polystyrene trithiocarbonate

Ab initio reversible addition–fragmentation chain transfer (RAFT) emulsion polymerization of styrene/butyl acrylate was investigated with the trithiocarbonate macro‐RAFT agent poly(acrylic acid)‐block‐polystyrene (PAA‐b‐PS) as a stabilizer and a RAFT agent. Influences of the amount of ammonium persulfate (APS), the amount of PAA‐b‐PS and the mass ratio of monomers on emulsion polymerization and film properties are discussed. The particle morphology exhibited spherical‐like structure with particles of about 90 nm in diameter and relatively narrow particle size distribution characterized using transmission electron microscopy and dynamic laser scattering. Fourier transform infrared and ¹H NMR spectra showed that the styrene/butyl acrylate emulsion was successfully synthesized. The monomer conversion increased initially with increasing amount of APS, from 0.4 up to 0.8 wt%, and then decreased. The particle size increased and its distribution decreased gradually with increasing amount of APS. The monomer conversion increased from 76.83 to 94.21% as the amount of PAA‐b‐PS increased from 3 to 4 wt%, and then decreased with further increase of PAA‐b‐PS. The particle size decreased and its distribution increased with increasing amount of PAA‐b‐PS. The water resistance and solvent resistance of the polymer films initially increased and then decreased with decreasing mass ratio of butyl acrylate to styrene. © 2014 Society of Chemical Industry     

Polystyrene‐block‐polylactide obtained by the combination of atom transfer radical polymerization and ring‐opening polymerization with a commercial dual initiator

A polystyrene (PS)‐b‐polylactide (PLA) block copolymer was prepared from the combination of atom transfer radical polymerization and ring‐opening polymerization with commercially available 2,2,2‐tribromoethanol as a dual initiator in a sequential two‐step procedure. Hydroxyl‐terminated polystyrene (PS‐OH)s with various molecular weights were first prepared with polydispersity indices lower than 1.3; these provided valuable macroinitiators for the polymerization of D,L ‐lactide. A block copolymer with a composition allowing the formation of hexagonally packed PLA cylinders in a PS matrix was then obtained. The PS‐b‐PLA thin films revealed, after vapor solvent annealing, a hexagonally packed organization of the PLA cylinders, which was oriented perpendicularly to the surface of the film. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Synthesis of poly(vinyl acetate)‐graft‐polystyrene and application to preparation of porous membranes

Poly(vinyl acetate)–TEMPO (PVAc–TEMPO) macroinitiators were synthesized by bulk polymerization of vinyl acetate in the presence of benzoyl peroxide (BPO) followed by termination with 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO). Radicals were mainly transferred to the acetoxy methyl groups in PVAc during the polymerization. The PVAc–TEMPO macroinitiators had several TEMPO‐dormant sites and styrene bulk polymerization with the macroinitiators produced poly(vinyl acetate)‐graft‐polystyrene (PVAc‐g‐PS). All the TEMPO‐dormant sites of PVAc–TEMPO macroinitiators participated in the styrene polymerization with almost equal reactivity. Methanolysis of PVAc‐g‐PS broke the PS branches apart from the PVAc backbone chains. Hydrophobic or hydrophilic porous membranes with controlled pore size could be prepared by removing the PVAc domains or the PS domains from the graft copolymer. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1658–1667, 2001     

Preparation of well‐defined block copolymer having one polystyrene segment and another poly(styrene‐alt‐maleic anhydride) segment with RAFT polymerization

Block copolymers, polystyrene‐b‐poly(styrene‐co‐maleic anhydride), have been prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization technique using three different approaches: 1‐phenylethyl phenyldithioacetate (PEPDTA) directly as RAFT agent, mediated polystyrene (PS) block as the macromolecular PS‐RAFT agent and mediated poly(styrene‐maleic anhydride) (SMA) block with alternating sequence as the macromolecular SMA‐RAFT agent. Copolymers synthesized in the one‐step method using PEPDTA as RAFT agent possess one PS block and one SMA block with gradient structure. When the macromolecular RAFT agents are employed, copolymers with one PS block and one alternating SMA block can be produced. However, block copolymers with narrow molecular weight distribution (MWD) can only be obtained using the PS‐RAFT agent. The MWD deviates considerably from the typical RAFT polymerization system when the SMA is used as the RAFT agent. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of block copolymers from PDMS macroinitiators

The synthesis of polystyrene‐b‐polydimethylsiloxane‐b‐polystyrene (PSt‐b‐PDMS‐b‐PSt) copolymers is described. Commercially available difunctional PDMS containing vinylsilyl terminal species was reacted with hydrogen bromide resulting in the PDMS macroinitiators. The terminal alkyl bromide groups were then used as initiators for atom transfer radical polymerization (ATRP) to produce block copolymers. Using this technique, triblock copolymers consisting of a PDMS centre block and polystyrene terminal blocks were synthesized. ATRP of St from those macroinitiators showed linear increases in M_n with conversion, demonstrating the effectiveness of ATRP to synthesize a variety of inorganic/organic polymer hybrids. Copyright © 2004 Society of Chemical Industry     

Synthesis of graft copolymers. III. Polystyrene‐g‐poly(butyl acrylate)

Polystyrene (PS) chains functionalized with pendant 1,2‐bis(trimethylsilyloxy)tetraphenylethane (TPSE) groups are used as macroinitiators to initiate the polymerization of n‐butyl acrylate (BuA) to synthesize PS‐g‐poly(BuA) (PS‐g‐PBuA) copolymers at 130°C. The TPSE groups are known to function as initers in the polymerization of several vinyl monomers. The homolytic decomposition of TPSE results in a diphenylmethyl (DPM) radical attached to the main chain and a free DPM radical. The former is responsible for the polymerization initiation and the latter momentarily stops the growth of the growing grafts by the formation of a dormant species. Unfortunately, side reactions like the combination between growing grafts take place and the polymerization can only be controlled in a limited range of conversion. The most appropriate conditions for the synthesis of PS‐g‐PBuA are reported to present their potential use as thermoplastic elastomers with relatively controlled structures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 19–26, 2002     

Modification of adhesive properties of a polyethylene film by photografting

Graft polymerization of acrylic acid from monomer solutions in water or in bulk onto low‐density polyethylene film substrate was carried out by the method of continuous process under UV radiation. Effects of the nature of photoinitiator on acrylic acid grafting was first studied. One PI₂ and two PI₁ photoinitiators were used. Benzophenone was then retained for the following study. The influence of photoinitiator and monomer concentration was investigated by determining polymerization kinetics and grafted polymer amount. A study of surface wetting and morphological structure was then carried out on a bulk system and as a function of the photoinitiator concentration. Finally, such surface modification was studied with respect to its effect on the adhesion of an acrylic stick on its surface. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2803–2811, 2004     

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     

RAFT synthesis of poly(N‐isopropylacrylamide) and poly(methacrylic acid) homopolymers and block copolymers: Kinetics and characterization

Reversible addition‐fragmentation chain transfer (RAFT) polymerization was used successfully to synthesize temperature‐responsive poly(N‐isopropylacrylamide) (PNIPAAm), poly(methacrylic acid) (PMAA), and their temperature‐responsive block copolymers. Detailed RAFT polymerization kinetics of the homopolymers was studied. PNIPAAm and PMAA homopolymerization showed living characteristics that include a linear relationship between M _n and conversion, controlled molecular weights, and relatively narrow molecular weight distribution (PDI < 1.3). Furthermore, the homopolymers can be reactivated to produce block copolymers. The RAFT agent, carboxymethyl dithiobenzoate (CMDB), proved to control molecular weight and PDI. As the RAFT agent concentration increases, molecular weight and PDI decreased. However, CMDB showed evidence of having a relatively low chain transfer constant as well as degradation during polymerization. Solution of the block copolymers in phosphate buffered saline displayed temperature reversible characteristics at a lower critical solution temperature (LCST) transition of 31°C. A 5 wt % solution of the block copolymers form thermoreversible gels by a self‐assembly mechanism above the LCST. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1191–1201, 2006     

Functionalization of multiwalled carbon nanotubes by reversible addition fragmentation chain-transfer polymerization

In this study, a new way was used to chemically synthesize polymer-connected MWNT nanocomposites. Reversible addition fragmentation chain-transfer (RAFT) agent was successfully grafted onto the surface of multiwalled carbon nanotubes (MWNTs). Polystyrene (PS) chains were successfully grafted from the surface of MWNTs via RAFT process by using RAFT agent immobilized on MWNTs. FTIR, XPS and TGA were used to determine chemical structure and the grafted PS quantities of the resulting products. TEM images of the samples provide direct evidence for the formation of a core-shell nanostructure, i.e. the MWNT coated with polymer layer and the solubility be improved.     

UV‐curable nanocomposites containing zirconium vinylphosphonate or zirconia

UV‐cured nanocomposite films were prepared from acrylic monomer and two types of nanomaterial: zirconium vinylphosphonate and zirconia, in the presence of a photoinitiator. The films were characterized by FTIR, SEM, and AFM. FTIR spectra showed the disappearance of band assigned to the CC group both of monomer and zirconium vinylphosphonate by polymerization and the presence of the phosphonate group in polymer. The influence of zirconium vinylphosphonate and zirconia content on thermooxidative degradation of polymeric films was studied by thermogravimetry. SEM and AFM images showed that nanomaterials are dispersed in polymer matrix with no macroscopic phase separation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011