Dynamic Viscosity of PEG:PEG‐ran‐PPG Blends through Stress Relaxation

Densities and viscosities of a series of blends of poly(ethylene glycol) (PEG) and poly(ethylene glycol‐ran‐propylene glycol) (PEG‐ran‐PPG) were measured at a temperature above the melting point. The density and viscosity data were fitted with analytical functions involving the volume fraction of PEG, ϕ_PEG. Stress relaxation curves for the pure components and blends were obtained through Monte Carlo (MC) simulations. A typical stress relaxation curve exhibits a fast mode that represents energetic‐interactions‐driven motion and a slow mode that originates from the entropy‐driven motion. Flory–Huggins interaction parameters (χ) for the blends are much smaller than the critical values (χ_critical). The calculation of χ and χ_critical provides important clues for polymer blend processing.

     

Preparation of Core‐Sheath Nanofibers from Conducting Polymer Blends

Summary: Core‐sheath nanofibers with conductive polyaniline as the core and an insulating polymer as the sheath were prepared by electrospinning of blends of polyaniline with either polystyrene or polycarbonate. These unique core‐sheath structures offer potential in a number of applications including nanoelectronics. When polyaniline was blended with poly(methyl methacrylate) and poly(ethylene oxide), only isolated domains of polyaniline in beadlike structures were formed. The phase morphology of electrospun fibers is thought to be dependent on the high‐surface tension of the solution and the molecular weight of the polymers. Incompatibility of the polymers and low molecular weight of compositions played a key role in the formation of core‐sheath structures, as opposed to co‐continuous morphologies.

TEM image of electrospun polyaniline/polystyrene nanofiber after staining by OsO₄. The dark regions are polyaniline.     

Modeling and Simulation of the Crystallization Behavior of Polymer Melts in the Hollow‐Profile Extrusion Process Using the Coexistence Model of Spherulite and Shish‐Kebab

The thermally and flow induced crystallization behavior of polymer melts has been investigated by using penalty finite element‐finite difference simulation with a decoupled solving algorithm. The coexistence model of spherulite and shish‐kebab is proposed to describe the evolution of crystallization kinetics process. The Schneider equation and Eder equation are adopted to discriminate the relative roles of the thermal and the flow effect on the crystallization behavior. The proposed mathematical model and numerical method have been successfully applied to the investigation of crystallization behavior in the hollow‐profile extrusion process. Both the evolution of crystalline size within the extrusion die and the effects of processing conditions on the crystallization kinetics process are discussed.

     

Copolymerization of Ethylene with Sterically Hindered 3,3‐Dimethyl‐1‐Butene Using a Chain‐Walking Pd‐Diimine Catalyst

In this Communication, the copolymerization of ethylene with a sterically hindered α‐olefin comonomer, γ‐trisubstituted 3,3‐dimethyl‐1‐butene (DMB), using a chain‐walking Pd‐diimine catalyst, [(ArNC(Me) (Me)CNAr)Pd(CH₃)(NCMe)]SbF₆ (Ar2,6‐(iPr)₂C₆H₃) ( 1 ) is reported. In spite of its high steric bulkiness in the close proximity of the double bond, appreciable DMB incorporations (up to 3 mol‐%) are successfully achieved in the copolymers. The chain microstructure of the copolymers is elucidated, and the effect of DMB incorporation on polymer topology and thermal properties are examined. This work thus demonstrates the high capability of the Pd‐diimine catalyst in incorporating sterically encumbered α‐olefins.

     

Large‐Scale Synthesis of Necklace‐Like Single‐Crystalline PbTiO3 Nanowires

Summary: We show in this communication that large‐scale necklace‐like single‐crystalline tetragonal perovskite PbTiO₃ nanowires can be obtained via a simple electrospinning method. The morphology and the crystal structure are investigated by SEM, XRD, and HRTEM. The length of the necklace‐like PbTiO₃ nanowires is from tens to several tens of micrometers, the wider the diameter of it is between 100 and 200 nm and the thinner the part is between 20 and 50 nm. The necklace‐like PbTiO₃ nanowires exhibit high surface photovoltage under the action of external electric field, which is probably applicable in displaying photoelectric devices of heterojunction structure.

SEM image of the electrospinning necklace‐like PbTiO₃ nanowires.     

Cross‐Linked Conjugated Polymers for Achieving Patterned Three‐Color and Blue Polymer Light‐Emitting Diodes with Multi‐Layer Structures

Reactions between the ethylene groups in the backbone of conjugated polymers under UV illumination and heat treatment result in the cross‐linking of the main polymer chains. The cross‐linking leads to two simultaneous results in the polymer: excellent solvent resistance and increased bandgap. Using this reaction, three‐color polymer light‐emitting diodes (PLEDs) with a multi‐layer structure can be easily realized by a dry photo‐pattern in an active‐gas‐free environment. Multi‐layer blue devices with dramatically enhanced efficiency can also be achieved conveniently.

     

Synthesis of POSS‐Functionalized Polyisobutylene via Direct Initiation

POSS‐functionalized polyisobutylenes (PIBs) were synthesized by carbocationic polymerization using an epoxy‐POSS/TiCl₄ initiating system in hexane/methyl chloride (60:40 v/v) solvent mixture at −80 °C. ¹H NMR spectroscopy verified the incorporation of one epoxy‐POSS per polymer chain. Light scattering and TEM analysis demonstrated the formation of 50–100 nm sized aggregates and micron‐sized clusters.

     

Micelles‐Encapsulated Microcapsules for Sequential Loading of Hydrophobic and Water‐Soluble Drugs

Layer‐by‐layer (LbL) assembly was conducted on CaCO₃ microparticles pre‐doped with polystyrene‐block‐poly(acrylic acid) (PS‐b‐PAA) micelles, and resulted in micelles encapsulation in the microcapsules after core removal. Distribution of the micelles in the templates and capsules was characterized by transmission electron microscopy and confocal laser scanning microscopy. The micelles inside the capsules connected with each other to form a chain and network‐like structure with a higher density near the capsule walls. The hydrophobic PS cores were then able to load small uncharged hydrophobic drugs while the negatively charged PAA corona could induce spontaneous deposition of water‐soluble positively charged drugs such as doxorubicin.

     

Emulsion‐Induced Ordered Microporous Films Based on Micelles of Amphiphilic Poly(ethylene oxide)‐block‐Poly(methyl methacrylate) Diblock Copolymers

Well‐defined PEO‐b‐PMMA was prepared, initiated by macroinitiator PEO‐Br, by means of ATRP, where esterification of the terminal hydroxyl group of PEO with 2‐bromoisobutyryl bromide yielded a macroinitiator PEO‐Br. Highly ordered microporous films (hexagonal pattern) were constructed by emulsion micelles of such amphiphilic diblock copolymer formed from a solution with CHCl₃/H₂O/THF = 100:5:10 (v/v). We also constructed the microporous films using diblock copolymer by the current water‐assisted method.

     

Block‐Copolymer‐Assisted Solubilization of Carbon Nanotubes and Exfoliation Monitoring Through Viscosity

Summary: The use of the block copolymers polystyrene‐block‐poly(ethylene oxide) and poly(methyl methacrylate)‐block‐poly(ethylene oxide) is described to assist the direct solubilization of single‐walled carbon nanotubes (SWNTs) into water under ultrasonic irradiation. As compared to surfactants and homopolymers, the block copolymer systems may offer the potential of additional unique morphologies through self‐assembly. TEM and AFM analyses of solution‐cast samples indicate exfoliation and wetting of the SWNTs by the block copolymer. With increasing duration of ultrasonic irradiation, an increase in solution viscosity is initially found, which suggests that it is a convenient indicator of the progress of exfoliation of the SWNTs. With continued intense ultrasonic irradiation, the solution viscosity may decrease apparently because of damage/breakage of the SWNTs.

Schematic of the interaction of the PMMA‐b‐PEO block copolymer with the single‐walled carbon nanotubes and the specific viscosity of the system in aqueous solution as a function of sonication time: results from using an ultrasound bath (‐‐‐‐▪‐‐‐‐) or an ultrasound horn (—▴—).     

Halogen‐Free Polyarylphosphonates and Polyelectrolyte Membranes for PEMFC by Nickel‐Catalyzed Phosphonylation with Silylated Phosphates

Summary: The nickel‐catalyzed arylphosphonylation with tris(trimethylsilyl) phosphite (TMSP) is applied to brominated high‐performance (HP) polymers in weakly coordinating high temperature solvents. At elevated temperatures, this affords halogen‐free, soluble, phosphonic acid‐functionalized polyelectrolytes and an unprecedented control of the degree of phosphonylation (ds_P). Brominated polysulfone (PSU) of various degrees of bromination (ds_Br) has been phosphonylated with TMSP in diphenyl ether at 200 °C in the presence of 1–10 mol‐% NiCl₂. Upon methanolysis, arylphosphonic PSU with ds_P up to 223 mol‐% is obtained in near quantitative bromine conversion. Catalyst residues are readily removed during methanolysis. This very versatile two‐step process affords soluble arylphosphonic polymers for casting tough membrane films. In contrast to sulfonated PSU, the arylphosphonic PSU membranes exhibit improved thermal and chemical stabilities, combined with far lower water swelling in accordance with the demands of polyelectrolyte membrane fuel cell (PEMFC) applications.

Mass swelling (sw_M) in water of sulfonated (A–C) and phosphonylated PSU (D).     

Metal‐Free Activation in the Anionic Ring‐Opening Polymerization of Cyclopropane Derivatives

The successful activation observed when using Bu^tP₄ phosphazene base and thiophenol or bisthiols for the anionic ring opening polymerization (ROP) of di‐n‐propyl cyclopropane‐1,1‐dicarboxylate is described. Well‐defined monofunctional or difunctional polymers with a very narrow molecular weight distribution were obtained through a living process. Quantitative end‐capping of the propagating malonate carbanion was accessible by using either an electrophilic reagent such as allyl bromide or a strong acid such as HCl. Kinetics studies demonstrated a much higher reactivity compared to the conventional route using alkali metal thiophenolates.

     

Synthesis of Folic Acid Functionalized PLLA‐b‐PPEGMA Nanoparticles for Cancer Cell Targeting

Poly(L ‐lactic acid)‐block‐poly(poly(ethylene glycol) monomethacrylate) (PLLA‐b‐PPEGMA) has been prepared by the ring‐opening polymerization of lactide with a double‐headed initiator, 2‐hydroxyethyl 2′‐methyl‐2′‐bromopropionate (HMBP), followed by atom transfer radical polymerization (ATRP) of poly(ethylene glycol) monomethacrylate (PEGMA). PLLA‐b‐PPEGMA nanoparticles with encapsulated Fe₃O₄ are prepared by a solvent evaporation/extraction technique, and then further functionalized with folic acid, a cancer targeting ligand. Our results show that such functionalized PLLA‐b‐PPEGMA nanoparticles have good potential as carriers for targeted drug delivery in cancer treatment.

     

Thermoreversibly Crosslinked Poly(ε‐caprolactone) as Recyclable Shape‐Memory Polymer Network

A new concept to build shape memory polymers (SMP) combining outstanding fixity and recovery ratios (both above 99% after only one training cycle) typical of chemically crosslinked SMPs with reprocessability restricted to physically crosslinked SMPs is demonstrated by covalently bonding, through thermoreversible Diels–Alder (DA) adducts, star‐shaped poly(ε‐caprolactones) (PCL) end‐functionalized by furan and maleimide moieties. A PCL network is easily prepared by melt‐blending complementary end‐functional star polymers in retro DA regime, then by curing at lower temperature to favour the DA cycloaddition. Such covalent network can be reprocessed when heated again at the retro DA temperature. The resulting SMP shows still excellent shape memory properties attesting for its good recyclability.

     

Fabrication of Highly Photoluminescent TiO2/PPV Hybrid Nanoparticle‐Polymer Fibers by Electrospinning

In this study, we have synthesized highly photoluminescent TiO₂/poly (phenylene vinylene) (PPV) hybrid nanoparticle‐polymer fibers by electrospinning a PPV precursor added to a TiO₂ sol‐gel solution. The diameters of the hybrid fibers ranged from 100–300 nm and the average size of TiO₂ nanoparticles within the fibers was 10–60 nm. FT‐IR analysis indicated that a new band around 1 632 cm⁻¹ assigned to the Ti O C vibration appeared, which resulted in the stronger luminance of the fluorescence of the TiO₂/PPV hybrid fibers compared to free standing PPV nanofibers.

     

Microwave‐Assisted Ring‐Opening Polymerization of ε‐Caprolactone in the Presence of Ionic Liquid

Summary: Microwave‐assisted ring‐opening polymerization of ε‐caprolactone in the presence of 1‐butyl‐3‐methylimidazolium tetrafluoroborate ionic liquid using zinc oxide as a catalyst is investigated. By adding 30 wt.‐% ionic liquid, poly(ε‐caprolactone) with a weight‐average molar mass of 28 500 g · mol⁻¹ is obtained at 85 W for 30 min. The results indicate that the polymerization could be efficiently enhanced in the presence of ionic liquids under microwave irradiation because ionic liquids can effectively absorb microwave energy.

     

A Facile Strategy for Preparation of α‐Heterobifunctional Polystyrenes with Well‐Defined Molecular Weight

A facile strategy for synthesis of α‐heterobifunctional polystyrenes is reported. The novel functional polystyrenes have been successfully synthesized via a combination of atom transfer radical polymerization (ATRP) and chemical modification of end‐functional groups. First, ε‐caprolactone end‐capped polystyrenes with controlled molecular weight and low polydispersity were prepared by ATRP of styrene using α‐bromo‐ε‐caprolactone (αBrCL) as an initiator. Then, removal of the terminal bromine atom was performed with iso‐propylbenzene in the presence of CuBr/PMDETA. Finally, ring‐opening modifications of the caprolactone group were carried out with amines, n‐butanol and H₂O to produce novel polystyrenes containing two different functional groups at one end.