pH Responsive Polymeric Brush Nanostructures: Preparation and Characterization by Scanning Probe Oxidation and Surface Initiated Polymerization

pH‐responsive PHEMA‐based polymeric nanostructures were grown in a controlled manner by ATRP‐based surface‐initiated polymerization. Initiator nanopatterns were obtained on silicon wafers covered with OTS resists made by AFM scanning probe oxidation lithography. AFM images confirmed isolated grafting of stimuli‐responsive hedge and dot brush structures exhibiting dimensions corresponding to a few tens of chains.

     

Strategy for Better Ordering in Diblock Copolymer Based Nanocomposites

A simple approach to improve the structural ordering in block copolymer/nanoparticle nanocomposites is presented. It is to blend a small molecular weight homopolymer with the composites, which can uniformly swell the preferred domain where the nanoparticles locate and increase the conformational entropy of the domain. Consequently, the interfaces between the block copolymer domains become smooth that improves the long range order in the nanocomposites. Furthermore, the uniform swelling of the preferred domain by the homopolymer will allow higher loading of nanoparticles without adversely affecting the long range order.

     

Fabrication of Biomimetic Superhydrophobic Coating with a Micro‐Nano‐Binary Structure

Summary: A superhydrophobic coating was facilely fabricated in one step by casting bisphenol A polycarbonate (PC) solution under moisture. Vapor‐induced phase separation occurred during the solidifying process and a rough surface with a micro‐nano‐binary structure (MNBS) similar to the microstructure shown on lotus leaf was formed.

SEM image of a single micro‐flower.     

Synthesis of Multinuclear Pyridylimine Based Palladium(II) Complexes with a Functionalized Star Polystyrene Core and Evaluation of Their Catalytic Activity Towards Ethylene Oligomerization

Summary: The synthesis of a novel series of multi‐nuclear macroligated pyridylimine based palladium(II) complexes conjugated to a synthetic star polymer core has been well‐described. Star shaped polystyrene with a finite number of arms were prepared by atom transfer radical polymerization (ATRP) and the chain ends were chemically modified in order to introduce the desired end functionality. Utilizing this polymer as organic supports for pyridylimine‐based ligands, palladium(II) complexes were synthesized. On activating with methylaluminoxane (MAO), this complex showed substantially high activity towards ethylene oligomerization, producing C₄ and C₆ compositions as major products. The plausible mechanistic insight concerning the process of ethylene oligomerization is also broached.

An example of trinuclear pyridylimine based palladium(II) complex having a functionalized star polystyrene core.     

Polypeptoids by Living Ring‐Opening Polymerization of N‐Substituted N‐Carboxyanhydrides from Solid Supports

The nucleophilic living ring‐opening polymerization of N‐substituted glycine N‐carboxyanhydrides using solid‐phase synthesis resins is reported. By variation of experimental parameters, products with near Poisson distributions are obtained. As opposed to reversible deactivation radical polymerization, the living polymerization is demonstrated to be viable to high monomer conversion and through multiple monomer addition steps. Successful preparation of a multiblock copolypeptoid is proof for a highly living and robust character of the solid‐phase peptoid polymerization.

     

Sequential Polymer Precipitation of Core–Shell Microstructured Composites with Giant Permittivity

Polymeric core–shell microstructures have been constructed through a new method, namely sequential precipitation, which is intrinsically a self‐assembly and phase separation process. High‐quality poly(vinyldene fluoride)–polycarbonate–lithium perchlorate composite films with spherical core–shell microstructures have been prepared and determined to consist of conducting cores and insulating shells. Because of the percolation effect, the resulting materials present a dielectric constant as high as 10⁴–10⁷ at the threshold.

     

Synthesis of Poly(ethylene oxide)s Bearing Functional Groups along the Chain

Well‐defined poly(ethylene oxide)s (PEOs) bearing reactive sites regularly distributed along the chain have been synthesized by the polycondensation of PEO containing a central tertiary amino group with dichloromethane, followed by quaternization with suitable reagents to obtain polyzwitterionic or cationic PEOs with alkyl, allyl, or fluorocarbon pendant groups. The pendant allyl groups have been converted into primary amino groups by reaction with 2‐aminoethanethiol hydrochloride to obtain polyamino‐functionalized PEO.

Polyfunctional PEOs bearing different pendant groups.     

Acrylic,Elastomeric, Particle‐Dispersed Epoxy‐Clay Hybrid Nanocomposites: Mechanical Properties

Summary: Nanocomposites were formulated by curing a sonicated mixture of epoxy resin, C18 clay, and acrylic rubber dispersants. At 5.5 phr (parts per hundred) organoclay loading and a rubber concentration of 15 phr, the tensile‐failure strain of the nanocomposite was found to be higher than that of epoxy nanocomposite, rubber‐dispersed epoxy, and pristine epoxy. A plausible mechanism for improvement of the failure strain of nanocomposites is proposed.

Stress strain curves of filled and unfilled epoxy specimen.     

Existence of Two Different Isotropic Phases as a Reason for Bistable Phase Behavior of an LC Side‐Chain Polymethacrylate

An isotropic melt of a chiral side‐chain polymethacrylate was studied by electric birefringence technique. A phase transition between two different isotropic phases was detected by Kerr effect and confirmed by WAXS measurements. The obtained experimental data can explain the previously reported bistable phase behavior of the polymer, as conventional Sm A phase is formed in slow cooling whereas a TGB‐like, optically isotropic mesophase in fast cooling.

     

Poly(2,5‐thienylene vinylene) in Nano Shapes by CVD Polymerization

Poly(2,5‐thienylene vinylene) (PTV), an insoluble conjugated polymer, can be readily prepared in various shapes of different nanodimensions by the chemical vapor deposition polymerization of 2,5‐bis(chloromethyl)thiophene. The bischloromethyl monomer in the vapor phase is activated at 600 °C. The activated monomer vapor is deposited at room temperature on the surface of various substrates to prepare polymeric films, fibers, tubes etc., which are then thermally converted into PTV. PTV thin films can be carbonized thermally to produce graphitic compositions that contain sulfur atoms. Electrical conductivities of FeCl‐doped PTV and carbonized films are reported.

     

Laccase‐Catalyzed Oxidative Polymerization of Phenols

Laccase‐catalyzed oxidative polymerization of phenol and its derivatives has been performed in aqueous organic solvents at room temperature in air. Laccase derived from Pycnoporus coccineus efficiently induced the polymerization to produce polyphenols consisting of a mixture of phenylene and oxyphenylene units. The unit ratio of the polymer could be precisely controlled by selection of the solvent and the monomer substituent.

     

pH‐Responsive PEG‐Poly(β‐amino ester) Block Copolymer Micelles with a Sharp Transition

Summary: A pH‐sensitive block copolymer is synthesized by step polymerization and its pH‐sensitive micellization‐demicellization behavior is studied. This polymer has a hydrophilic MPEG (shell) and hydrophobic but pH‐sensitive poly(β‐amino ester) (core), which can form a self‐assembled micelle. As confirmed by fluorescence spectroscopy and dynamic light scattering (DLS), this polymer shows a sharp pH‐sensitive micellization‐demicellization behavior. It is confirmed that the pH sensitivity is affected by the molecular weight ratio between the MPEG and poly(β‐amino ester).

Plots of the intensity ratio I₃₃₇/I₃₃₄ (from pyrene excitation spectra): a) vs. pH for copolymer samples and b) vs. log (concentration) for M1.     

Self‐Consistent Field Modeling of Three‐Dimensional Morphologies of Branched Lipid Surfactant at Air‐Water Interface

Three‐dimensional mesoscopic morphologies and the thermodynamics of structural phase transitions of amphiphilic lipids at air‐water interfaces are studied using self‐consistent field theory. Changing the relative amount of lipids in the system led to a series of 3D morphologic phases with varying average interfacial area per molecule, mimicking a compression of the model membranes. Membranes of both saturated and unsaturated lipids undergo a transition from cylindrical micelle to lamella when the lipid content in the system increases from 2% to about 19–20%. With further increase in the lipid content, saturated lipids first develop non‐uniform quasi‐2D distributions in the lamella and then gradually transform into a hybrid morphology containing quasi‐planar lamellae. In contrast, unsaturated lipids develop reverse‐micellar morphologies.

     

On the Statistical Nonliving Nature of the Cationic Ring‐Opening Copolymerization of Oxetane with Tetrahydropyran

The copolymerization system of oxetane and tetrahydropyran is reinterpreted with the aid of computer simulations. The original claim that this system is a “living” and/or controlled pseudoperiodic copolymerization 1 is not confirmed by the simulation results. It is suggested that the formation of branched oxonium cations and the statistical nature of THP incorporation are the reasons for the observed discrepancies between the simulation results and experimental data.

     

Tertiary Amine — Enhanced Activity of ATRP Catalysts CuBr/TPMA and CuBr/Me6TREN

Tertiary amines were found to remarkably enhance the catalytic activity of ATRP catalysts CuBr/tris[(2‐pyridyl)methyl]amine and CuBr/tris[2‐(dimethylamino)ethylamine]. These two catalysts alone failed to polymerize MA, MMA, and styrene at reduced catalyst concentrations. With tertiary amines such as triethylamine both catalysts could mediate fast polymerizations of the three monomers in a controlled manner at as low as 1 mol‐% catalyst relative to initiator. A mechanism study showed that tertiary amines reduced copper(II) complexes to active copper(I) complexes.

     

Synthesis and Self‐Assembly of Amphiphilic Diblock Copolymers using a Fluorescently Labeled N‐Alkoxyamine Initiator

Summary: An initiator for nitroxide mediated ‘living’ free radical polymerization was prepared with a fluorescent tag attached to the initiating alkyl radical terminus. This was used to synthesize amphiphilic poly(acrylic acid)‐block‐polystyrene diblock copolymers, which self assembled in a tetrahydrofuran/buffer solution to form structures that are visible by fluorescence.

     

Effect of an Organically Modified Nanoclay on Low‐Surface‐Energy Materials of Polybenzoxazine

Novel low surface free energy materials of polybenzoxazine/organically modified silicate nanocomposites have been prepared and characterized. The CPC (cetylpyridinium chloride)/clay10%/poly(3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine) (PP‐a) material possesses an extremely low surface free energy (12.7 mJ · m⁻²) after 4 h curing at 200 °C, which is even lower than that of poly(tetrafluoroethylene) (22.0 mJ · m⁻²) calculated on the basis of the three‐liquid geometric method. X‐Ray photoelectron spectroscopy (XPS) shows a higher silicon content on the surface of the nanocomposites than for an average composition, which implies that the clay is more preferentially enriched on the outermost layer. In addition, the glass transition temperature (T_g) of the polybenzoxazine (PP‐a) in the nanocomposite is 22.6 °C higher and its thermal decomposition temperature is also 31.5 °C higher than the pure PP‐a. This finding provides a simple way to prepare low surface energy and high thermal stability materials.

     

Silyl‐Substituted Poly(thienylenevinylene) via Heteroaromatic Dehydrohalogenation Polymerization

A long alkylsilyl group was attached to a thiophene ring system to overcome the instability of 2,5‐bis(halomethyl)thiophene monomers, by imparting steric hindrance and electronic delocalization. The resulting stable monomer could be used directly to prepare low‐band‐gap poly(thienylenevinylene) (1.57 eV) through heteroaromatic dehydrohalogenation polymerization.