Synthesis of SET–LRP‐induced galactoglucomannan‐diblock copolymers

Polysaccharides are biorenewable and biodegradable starting materials for the development of functional materials. The synthesis of a monofunctional macroinitiator for single electron transfer‐living radical polymerization was successfully developed from a wood polysaccharide‐O‐acetyl galactoglucomannan (GGM) using a beforehand synthesized amino‐functional α‐bromoisobutyryl derivative applying reductive amination. The GGM macroinitiator was employed to initiate a controlled radical polymerization of [2‐(methacryloyloxy)ethyl]trimethylammonium chloride (MeDMA), methyl methacrylate (MMA), and N‐isopropylacrylamide (NIPAM) using Cu⁰/Me₆‐Tren as a catalyst. The either charged or amphiphilic GGM‐b‐copolymers with different chain lengths of the synthetic block were successfully synthesized without prior hydrophobization of the GGM chain and dimethyl sulfoxide (DMSO) or DMSO/water mixtures were used as solvents. This novel synthetic approach may find untapped potentials particularly for the development of polysaccharide‐based amphiphilic additives for cosmetics or paints and for the design of novel temperature or pH responsive polymers with such potential applications as in drug delivery systems or in biocomposites. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5100–5110     

Poly(phenylene oxide) copolymer anion exchange membranes

Poly(phenylene oxide) block and random copolymers are synthesized by oxidative polymerization of 2,6-dimethylphenol and 2,6-diphenylphenol for potential alkaline exchange membrane application. The copolymers are functionalized on the methyl substituted repeat units through a two-step process to produce pendent quaternary ammonium cationic groups. The amount of quaternary ammonium cations and the ion exchange capacity are quantified through titration measurements. Ionic conductivity of the copolymer membranes is measured by electrochemical impedance spectroscopy. Block copolymers show increased bromide conductivity at higher ion exchange capacities compared with the random copolymer analogs. The bromide conductivity for a block copolymer film with an ion exchange capacity of 1.27 mequiv/g reaches 26 mS/cm at 90 °C and 95% relative humidity. The hydroxide conductivity for the same film was measured to be 84 mS/cm at 80 °C and 95% relative humidity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1770–1778, 2013     

Biocompatible and pH‐responsive triblock copolymer mPEG‐b‐PCL‐b‐PDMAEMA: Synthesis,self‐assembly,and application

A series of well‐defined amphiphilic triblock copolymers [polyethylene glycol monomethyl ether]‐block‐poly(ε‐caprolactone)‐block‐poly[2‐(dimethylamino)ethyl methacrylate] (mPEG‐b‐PCL‐b‐PDMAEMA or abbreviated as mPEG‐b‐PCL‐b‐PDMA) were prepared by a combination of ring‐opening polymerization and atom transfer radical polymerization. The chemical structures and compositions of these copolymers have been characterized by Fourier transform infrared spectroscopy, ¹H NMR, and thermogravimetric analysis. The molecular weights of the triblock copolymers were obtained by calculating from ¹H NMR spectra and gel permeation chromatography measurements. Subsequently, the self‐assembly behavior of these copolymers was investigated by fluorescence probe method and transmission electron microscopy, which indicated that these amphiphilic triblock copolymers possess distinct pH‐dependent critical aggregation concentrations and can self‐assemble into micelles or vesicles in PBS buffer solution, depending on the length of PDMA in the copolymer. Agarose gel retardation assays demonstrated that these cationic nanoparticles can effectively condense plasmid DNA. Cell toxicity tests indicated that these triblock copolymers displayed lower cytotoxicity than that of branched polyethylenimine with molecular weight of 25 kDa. In addition, in vitro release of Naproxen from these nanoparticles in pH buffer solutions was conducted, demonstrating that higher PCL content would result in the higher drug loading content and lower release rate. These biodegradable and biocompatible cationic copolymers have potential applications in drug and gene delivery. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1079–1091, 2010     

Synthesis and properties of high‐molecular‐weight stereo di‐block polylactides with nonequivalent D/L ratios

Di‐stereoblock polylactides (di‐sb‐PLA: PLLA‐b‐PDLA) having high molecular weight (M_n > 100 kDa) were successfully synthesized by two‐step ring‐opening polymerization (ROP) of L ‐ and D ‐lactides using tin(2‐ethylhexanoate) as a catalyst. By optimizing the polymerization conditions, the block sequences were well regulated at non‐equivalent feed ratios of PLLA and PDLA. This synthetic method consisted of three stages: (1) polymerization of either L ‐ or D ‐lactide to obtain a PLLA or PDLA prepolymer with a molecular weight less than 50 kDa, (2) purification of the obtained prepolymer to remove residual lactide, and (3) polymerization of the enantiomeric lactide in the presence of the purified prepolymer. Their ¹³C and ³¹P NMR spectra of the resultant di‐sb‐PLAs strongly supported their di‐stereo block structure. These di‐sb‐PLAs, having weight‐average molecular weights higher than 150 kDa, were fabricated into polymer films by solution casting and showed exclusive stereocomplexation. The thermomechanical analysis of the films revealed that their heat deformation temperature was limited probably because of their low crystallinity owing to the non‐equivalent PLLA/PDLA ratio. The blend systems of the di‐sb‐PLAs having complementary stereo‐sequences (the one with a long PLLA block and the other with long PDLA block) were also prepared and characterized to enhance the sc crystallinity. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 794–801, 2010     

Thermoresponsive brush copolymers with poly(propylene oxide‐ran‐ethylene oxide) side chains via metal‐free anionic polymerization “grafting from” technique

Thermoresponsive brush copolymers with poly(propylene oxide‐ran‐ethylene oxide) side chains were synthesized via a “grafting from” technique. Poly(p‐hydroxystyrene) was used as the backbone, and the brush copolymers were prepared by random copolymerization of mixtures of oxyalkylene monomers, using metal‐free anionic ring‐opening polymerization, with the phosphazene base (t‐BuP₄) being the polymerization promoter. By controlling the monomer feed ratios in the graft copolymerization, two samples with the same side‐chain length and different compositions were prepared, both of which possessed high molecular weights and low molecular weight distributions. The results from light scattering and fluorescence spectroscopy indicated that the brush copolymers in their dilute aqueous solutions were near completely solvated at low temperature and underwent slight intramolecular chain contraction/association and much more profound intermolecular aggregation at different stages of the step‐by‐step heating process. Above 50 °C, very turbid solutions, followed by macrophase separation, were observed for both of the samples, which implied that it was difficult for the brush copolymers to form stable nanoscopic aggregates at high temperature. All these observations were attributed, at least partly, to the distribution of the oxyalkylene monomers along the side chains and the overall brush‐like molecular architecture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2320–2328, 2010     

Stereospecific styrene polymerization and ethylene–styrene copolymerization with titanocenes containing a pendant amine donor

A series of monocyclopentadienyl titanium complexes containing a pendant amine donor on a Cp group ( A = CpTiCl₃, B = Cp^NTiCl₃, C = Cp^NTiCl₂TEMPO, for Cp = C₅H₅, Cp^N = C₅H₄CH₂CH₂N(CH₃)₂, and TEMPO = 2,2,6,6‐tetramethylpiperidine‐N‐oxyl) are investigated for styrene homopolymerization and ethylene–styrene (ES) copolymerization. When activated by methylaluminoxane at 70 °C, complexes with the amine group ( B and C ) are active for styrene homopolymerization and afford syndiotactic polystyrene (sPS). The copolymerizations of ethylene and styrene with B and C yield high‐molecular weight ES copolymer, whereas complex A yields mixtures of sPS and polyethylene, revealing the critical role that the pendant amine has on the polymerization behavior of the complexes. Fractionation, NMR, and DSC analyses of the ES copolymers generated from B and C suggest that they contain sPS. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1579–1585, 2010     

Hydrogen bonding interactions,crystallization, and surface hydrophobicity in nanostructured epoxy/block copolymer blends

Hydrogen bonding interactions, phase behavior, crystallization, and surface hydrophobicity in nanostructured blend of bisphenol A‐type epoxy resin (ER), for example, diglycidyl ether of bisphenol A (DGEBA) and poly(ε‐caprolactone)‐block‐poly(dimethyl siloxane)‐block‐poly(ε‐caprolactone) (PCL–PDMS–PCL) triblock copolymer were investigated by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, transmission electron microscopy, small‐angle X‐ray scattering, and contact angle measurements. The PCL–PDMS–PCL triblock copolymer consisted of two epoxy‐miscible PCL blocks and an epoxy‐immiscible PDMS block. The cured ER/PCL–PDMS–PCL blends showed composition‐dependent nanostructures from spherical and worm‐like microdomains to lamellar morphology. FTIR study revealed the existence of hydrogen bonding interactions between the PCL blocks and the cured epoxy, which was responsible for their miscibility. The overall crystallization rate of the PCL blocks in the blend decreased remarkably with increasing ER content, whereas the melting point was slightly depressed in the blends. The surface hydrophobicity of the cured ER increased upon addition of the block copolymer, whereas the surface free energy (γ_s) values decreased with increasing block copolymer concentration. The hydrophilicity of the epoxy could be reduced through blending with the PCL–PDMS–PCL block copolymer that contained a hydrophobic PDMS block. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 790–800, 2010     

Improvement in estimating the population mean in simple random sampling using information on auxiliary attribute

This paper proposes some estimators for the population mean by adapting the estimator in Singh et al. (2008) [5] to the ratio estimators presented in Kadilar and Cingi 2006 [2]. We obtain mean square error (MSE) equation for all proposed estimators, and show that all proposed estimators are always more efficient than ratio estimator in Naik and Gupta (1996) [3], and Singh et al. (2008) [5]. The results have been illustrated numerically by taking some empirical population considered in the literature.     

Synthesis and characterization of poly(vinylidene fluoride‐co‐chlorotrifluoroethylene)‐grafted‐poly(acrylonitrile) via single electron transfer–living radical polymerization process

Preparation of functional fluoromaterials through chemical modification of traditional fluoropolymers has been recognized as an economic and convenient strategy to expand the application areas of fluoropolymers. Poly(vinylidene fluoride‐co‐chlorotrifluoroethylene)‐grafted‐polyacrylonitrile (P(VDF‐co‐CTFE)‐g‐PAN) has been successfully synthesized via single electron transfer–living radical polymerization (SET–LRP) process initiated with macroinitiator P(VDF‐co‐CTFE) in the presence of trace amount of Cu(0)/tris(2(dimethylamino)ethyl)amine (Me₆‐TREN) in dimethyl sulfoxide (DMSO) at ambient temperature. The typical side reactions happened on P(VDF‐co‐CTFE) induced by the nitrogen‐containing solvents and high reaction temperature in atom transfer radical polymerization process could be avoided in SET–LRP process by using the mild reaction conditions. Well‐controlled polymerization features were observed under varied reaction conditions including the different reaction temperature, catalyst concentration, as well as monomer amount in feed. An induction period of 0.5–1.0 h in the polymerization procedure was observed at low temperature, which may be attributed to the Cu₂O from the surface of the Cu(0) powder. When Cu(0) catalyst is activated, the introduction period is eliminated. The polymerization rates were decelerated by adding excessive Me₆‐TREN for the formation of more stable CuCl₂/(Me₆‐TREN)₂. The structure of P(VDF‐co‐CTFE)‐g‐PAN was demonstrated by FTIR, NMR, DSC, and TGA. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012