Evaluation of different catalyst systems for bulk polymerization through “click” chemistry

“Click” chemistry is a frequently used technique in polymer chemistry for coupling polymer end groups to construct novel copolymer architectures and as a step-growth polymerization technique. In this study, the bulk polymerization of a diyne and a bisazide were achieved through the copper-catalyzed alkyne-azide 1,3-cycloaddition (CuAAC) with different catalysts, including the homogeneous catalyst Cu(PPh₃)₃Br and a heterogeneous Cu/C catalyst. The effects of different catalyst systems on the kinetics of the “click” polymerization were evaluated by differential scanning calorimetry (DSC) and oscillatory rheology. Additionally, the thermomechanical properties of resulting polymers were evaluated by temperature-ramp oscillatory rheology and thermal stabilities by thermogravimetry.     

Polymeric nanoparticles from macroscopic crystalline monomers by facile solid-state polymerization in supercritical CO2

When macroscopic crystalline monomers were polymerized by a free-radical solid-state reaction in the presence of supercritical CO₂ (scCO₂), the resultant products were found to be composed of unexpected nanoparticle morphologies. In particular, the solid-state polymerization (SSP) of amino acid based monomers, acryloyl-β-alanine (ABA) and methacryloyl-β-alanine (MBA), initiated by azobisisobutyronitrile in scCO₂ (at 65 °C and 34.5 MPa), produced corresponding polymers having aggregated spherical architectures. The average diameters of the PABA and PMBA particles were measured to be 94 and 102 nm, respectively. In addition, high molecular weight polymers (PMBA, M_w = 3.8 × 10⁵ g/mol) with a high yield (∼96%) were obtained. The microscopic investigation revealed that a unique particle formation mechanism was involved in the SSP in which large sized crystalline monomers were chipped into small pieces during the initial stage of polymerization and subsequently converted into nanoscale objects after 24 h.     

Production of titania nanoparticles by a green process route

The manufacture of heterogeneous catalysts and catalyst supports produces substantial amounts of nitrate containing aqueous effluent. The use of nitrate free precursors and an environmentally friendly process would change the manufacture so that the entire process of catalyst synthesis and use can be considered green. In this work the precipitation of titania acetylacetonate nanoparticles for use as catalytic supports using a supercritical carbon dioxide anti-solvent process was investigated over a range of conditions. The effects of 1) pressure, 2) temperature, 3) solution flowrate, 4) solution concentration of TiO(acac)₂ in methanol, 5) nozzle diameter and 6) CO₂/methanol flow ratio on the mean particle size and morphology were studied. Particle sizes between 27 and 78 nm were obtained and were generally string and branch-like with an amorphous nature. Pressure and temperature had little effect on the mean particle size. A decrease in the velocity of the solution flow rate led to an increase in mean particle size and to particles that exhibited greater interconnectivity. It was also observed that an increase in concentration of TiO(acac)₂ in methanol led to an increase in mean particle size. The process shows promise for the production of catalysts by an environmentally acceptable route.     

Polymer melt rheology with high-pressure CO2 using a novel magnetically levitated sphere rheometer

A magnetically levitated sphere rheometer (MLSR) designed to measure viscosity of fluids exposed to high-pressure carbon dioxide has been developed. This device consists of a magnetic sphere submerged inside a test fluid within a high-pressure housing and levitated at a fixed point. The housing is constructed from an optically transparent sapphire tube. The cylindrical tube can be moved vertically to generate a shear flow around the levitated sphere. The difference in magnetic force required to levitate the sphere at rest and under fluid motion can be directly related to fluid viscosity. Rheological properties, specifically zero shear viscosities, of transparent high-pressure materials can be measured to a precision of about 5% and over a wide range of viscosities. In addition, operation at constant pressure, in concentration regimes from a pure polymer to an equilibrated polymer/supercritical fluid solution, and at shear rates over several orders of magnitude is possible, eliminating many of the disadvantages associated with other high-pressure rheometers. Experiments performed at different temperatures with a poly(dimethylsiloxane) melt at atmospheric pressure are compared with data from a commercial Couette rheometer to demonstrate device sensitivity and viability. Measurements of a PDMS melt plasticized by high-pressure CO₂ are performed to illustrate the utility of the new rheometer under high-pressure conditions. Experimental data are obtained at 30 °C, for pressures up to 20.7 MPa and CO₂ concentrations reaching 30 wt%. Viscosity reductions of nearly two orders of magnitude compared with the pure polymer viscosity at atmospheric pressure are observed. Additionally, the effects of pressure on a polymer/CO₂ system are directly investigated taking advantage of the constant pressure operation mode of the MLSR. This allows us, for the first time in experiments of polymers with supercritical fluids, to decouple the effects of CO₂ concentration and pressure in a single device.     

Supercritical CO2 as an efficient medium for layered silicate organomodification: Preparation of thermally stable organoclays and dispersion in polyamide 6

In this study, the preparation of organoclays via a new process using supercritical carbon dioxide is described. This method turns out to be very efficient with various surfactants, in particular nonwater-soluble alkylphosphonium salts. The influence of the surfactant as well as of the clay nature on the thermal stability of the organoclay is evaluated by thermogravimetric analysis. Phosphonium-based montmorillonites are up to 90 °C more stable than ammonium-based montmorillonites. Moreover, the use of hectorite adds another 40 °C of thermal stability to the phosphonium-modified clays. These organomodified clays have been melt-blended with polyamide 6 and morphology as well as fire properties of the nanocomposites are discussed, in terms of influence of the stability of organoclays. For the first time, comparison of nanocomposites based on clay organomodified by ammonium and phosphonium salts of the very same structure is reported.     

Synthesis of PCL/clay masterbatches in supercritical carbon dioxide

Pre-exfoliated nanoclays were prepared through a masterbatch process using supercritical carbon dioxide as solvent and poly(?-caprolactone) as organic matrix. In situ polymerization of ?-caprolactone in the presence of large amount of clay was conducted to obtain these easily dispersible nanoclays, collected as a dry and fine powder after reaction. Dispersion of these pre-exfoliated nanoclays in chlorinated polyethylene was also investigated. All the results confirm the specific advantages of supercritical CO₂ towards conventional solvents for filler modification.     

In situ study of ionic conductivity for polyether-LiCF3SO3 electrolytes with subcritical and supercritical CO2

In situ measurements of the ionic conductivity were performed on polyethers, poly(ethylene oxide) (PEO) and poly(oligo oxyethylene methacrylate) (PMEO), with lithium triflate (LiCF₃SO₃) as crystalline and amorphous electrolytes, and at CO₂ pressures up to 20 MPa. Both PEO and PMEO systems in subcritical and supercritical CO₂ increased more than five fold in ionic conductivity at 40 °C composed to atmospheric pressure. The pressure dependence of the ionic conductivity for PEO electrolytes was positive under CO₂, and increased by two orders of magnitude under pressurization from 0 to 20 MPa, whereas it decreases with increasing pressure of N₂. The enhancement is caused by the plasticizing effect of CO₂ molecules that penetrate into the electrolytes.     

“Deactivation of copper electrode” in electrochemical reduction of CO2

Metallic Cu electrode can electrochemically reduce CO₂ to CH₄, C₂H₄ and alcohols with high yields as revealed by the present authors. Many workers reported that formation of CH₄ and C₂H₄ rapidly diminishes during electrolysis of CO₂ reduction. This paper shows that such deactivation of Cu electrode is reproduced with electrolyte solutions prepared from reagents used by these workers. Deactivated Cu electrodes recovered the electrocatalytic activity for CO₂ reduction by anodic polarization at −0.05 V versus she in agreement with the previous reports. Features of the deactivation depend greatly on the individual chemical reagents. Purification of the electrolyte solution by preelectrolysis with a Pt black electrode effectively prevents the deactivation of Cu electrode. Anode stripping voltammetry of Cu electrodes, which were deactivated during electrolysis of CO₂ reduction, showed anodic oxidation peaks at ca. −0.1 or −0.56 V versus she. The severer the deactivation of the Cu electrode was, the higher electric charge of the anodic peak was observed. It is presumed that some impurity heavy metal, originally contained in the electrolyte, is deposited on the Cu electrode during the CO₂ reduction, poisoning the electrocatalytic activity. On the basis of the potential of the anodic peaks, Fe²⁺ and Zn²⁺ are assumed to be the major contaminants, which cause the deactivation of the Cu electrode. Deliberate addition of Fe²⁺ or Zn²⁺ to the electrolyte solutions purified by preelectrolysis exactly reproduced the deactivation of a Cu electrode in CO₂ reduction. The amount of the deposited Fe or Zn on the electrode was below the monolayer coverage. Electrothermal atomic absorption spectrometry (etaas) showed that Fe originally contained in the electrolyte solution is effectively removed by the preelectrolysis of the solution. Mechanistic difference is discussed between Fe and Zn in the deterioration of the electrocatalytic property of Cu electrode in the CO₂ reduction. The concentration of the impurity substances originally contained in the chemical reagents as Fe or Zn is estimated to be far below the standard of the impurity levels guaranteed by the manufacturers. Presence of trimethylamine in the electrolyte solution also severely poisons a Cu electrode in the CO₂ reduction. It was concluded that the deactivation of Cu electrode in CO₂ reduction is not caused by adsorption of the products or the intermediates produced in CO₂ reduction.     

Grafting of polypropylene with N-cyclohexylmaleimide and styrene simultaneously using supercritical CO2

Monomer mixture of styrene (St) and N-cyclohexylmaleimide (ChMI) and initiator benzoyl peroxide (BPO) were first impregnated into isotactic polypropylene (iPP) films simultaneously using supercritical carbon dioxide (SC CO₂) as a solvent and swelling agent at 35.0 °C. The composites were obtained after the monomers were grafted onto the iPP matrix at 70 °C. The effects of various conditions, such as pressure, monomer concentration, and the molar ratio of the two monomers in the soaking process, on the composition of the composites were determined. The molar ratios of St to ChMI in the composites were estimated by Fourier transform infrared spectroscopy. The thermal properties, the morphology, and the mechanical properties of the composites were characterized by different techniques. The results demonstrated that the phase size of the grafted St-ChMI was very small and the phase boundary was very ambiguous. The composites had better thermal stability than the original iPP film. The Young's modulus and tensile strength of the film increased continuously with increasing grafting percentage. The two grafted monomers in the composites had good synergetic effect.     

Synthesis and property of polystyrene particle with smart surface by emulsion polymerization using “giant” surfactant

The colloidal particles with switchable surfaces (i.e. smart surfaces) have attracted great attention for numerous potential industrial applications. We report here a novel approach for the fabrication of polymeric particles with smart surfaces by emulsion polymerization using “giant” surfactant. Specifically, the “giant” surfactant was obtained by incorporating poly(4-vinylpyridine) chains onto the one bulb of snowman-shaped polystyrene particles, and then used as emulsifier for the emulsion polymerization at pH = 2.00. The nearly monodisperse waxberry-like polystyrene particles were prepared with dual-size roughness surfaces, and the particulate film exhibited reversibly pH-switchable superhydrophobic property due to the pH-sensitivity of P4VP chains and the surface topology. This property enabled the particles could be used to effectively sequester hazardous anions from the wastewater.     

Cetirizine solubility in supercritical CO2 at different pressures and temperatures

A simple static technique was used to obtain the solubility of cetirizine in supercritical carbon dioxide. The solubility measurements were performed at temperatures and pressures ranging from 308.15 to 338.15 K and 160 to 400 bar, respectively; resulting in mole fractions in the 1.05 × 10⁻⁵ to 4.92 × 10⁻³ range. The Chrastil, Bartle, Kumar & Johnston and the Mendez-Santiago and Teja (MST) models were used to correlate the experimental data. The calculated solubilities showed good agreement with the experimental data in the temperature and pressure ranges studied.     

Fabrication of bulk nanocrystalline alumina–zirconia materials

Eutectic mixtures of alumina and zirconia have been successfully transformed to thick amorphous coatings and free-standing parts by plasma spraying. The as-sprayed material has very low open porosity and crystallizes when heated above 950 °C. Short annealing times at the crystallization temperature result in the formation of a very fine microstructure throughout the sample volume with average grain size below 15 nm. The fine nanocomposite structure was confirmed by transmission electron microscopy. High hardness and abrasion resistance of the as-sprayed materials are significantly improved upon annealing due to the nanocomposite structure, which makes the bulk nanocrystalline ceramic material attractive.     

Supercritical CO2 conditioning promotes γ-crystal formation in amorphous syndiotactic polystyrene during further heating

The conditioning history of amorphous syndiotactic polystyrene (sPS) in mild supercritical CO₂ (scCO₂) changes significantly the thermal behavior and crystal phase transformation of sPS in further thermal treatment by inducing the formation of helical segments. The results of differential scanning calorimetry and temperature-dependent Fourier transform infrared spectroscopy show that polymer chains are preferred to arrange into crystalline γ-form with helical conformation in the conditioned sPS by heating under ambient pressure. Thus, mixed γ-form and α-form with all-trans conformation are formed in the amorphous sPS after conditioning instead of α-form in the amorphous sPS without conditioning, and the formation of α-form is totally suppressed in the conditioned sPS having only γ-form of small degree of crystallinity.     

The application of a supercritical antisolvent process for sustained drug delivery

Supercritical processes for drug delivery system design have attracted considerable attention recently. This present work investigates the application of a supercritical antisolvent coating process for controlled drug release design. Hydrocortisone as the host drug particles and poly(lactide-co-glycolide) (PLGA) as the polymer carrier were selected as the model system for this purpose. In this research the drug particles were suspended in a polymer solution of dichloromethane. The suspension was then sprayed into supercritical CO₂ as an antisolvent. A parallel study of co-precipitation of the drug and polymer using the same supercritical antisolvent process at the same operating conditions was performed for comparison with the coating process. SEM images were used to characterize the drug particles before and after and the assay analysis was carried out using HPLC. The coated particles and co-precipitated particles were evaluated in terms of encapsulation efficiency and drug release profiles. The major advantage of this new approach is the ability to physically coat very fine (< 30 μm) particles without having to dissolve them in an organic solvent. It was found that higher polymer to drug ratios produced higher encapsulation efficiencies and the coated drug particles did show sustained release behavior. The co-precipitation of the drug and polymer (at the same operating conditions), however, did not exhibit any sustained release.     

Porous polymers prepared via high internal phase emulsion polymerization for reversible CO2 capture

A series of porous polymers with different pore volumes, pore sizes, and crosslinking densities were synthesized by high internal phase emulsion (HIPE) polymerization. The crosslinked polymerized HIPEs (polyHIPEs) were formed by the copolymerization of 4-vinylbenzyl chloride and divinylbenzene using water droplets in conventional or Pickering HIPEs as the templates. These porous materials were further modified by quaternization and ion exchange to introduce quaternary ammonium hydroxide groups. The resulting polyHIPEs were utilized as sorbents for reversible CO₂ capture from air using the humidity swing. The effect of pore structure on the CO₂ adsorption and desorption processes was studied. The polyHIPEs containing large pores and interconnected porous structures showed improved swing sizes and faster adsorption/desorption kinetics of CO₂ compared to a commercial Excellion membrane with similar functional groups.     

Surface-initiated controlled polymerization as a convenient method for designing functional polymer brushes: From self-assembled monolayers to patterned surfaces

Surface-functionalization mediated through “grafting from” methods is of considerable interest as means to tailor the chemical and physical properties of functional substrates in a reliable way. The resulting polymer brushes, obtained by a “grafting from” strategy, are composed of grafted polymer chains tethered from one of their extremities to a surface by a covalent bond. Tuning the molecular parameters of these polymeric brushes such as the nature of monomer, the grafting density, and the chain length as well as the design of micropatterned structures enables delicate modification of the properties of these substrates, paving the way to the development of functional surfaces. In this review, we highlight recent and most important approaches to form monolayers and to subsequently elaborate homogeneous and heterogeneous coatings of polymer brushes by surface-initiated polymerization. The control of initiator molecule assembly is particularly important for the final configuration of polymer brushes. We report the creation of homopolymers and block copolymers using major controlled polymerization techniques as well as lithographic techniques aiming at the design of polymeric (micro- or nano-) patterns.     

The Possibility of Reprocessing of Spent Nuclear Fuel Using Supercritical Fluids

For the first time, the possibility of dissolution of spent nuclear fuel from a nuclear power plant in liquid and supercritical carbon dioxide was demonstrated. As shown by the example of spent nuclear fuel, the dissolution and the extraction of actinides and fission products by solutions of tributyl phosphate and nitric acid adducts TBP(HNO₃)_1.8 in carbon dioxide can be used as one of the stages of spent nuclear fuel reprocessing.     

Development of new alumina-modified sorbents for CO2 sorption and regeneration at temperatures below 200 °C

A new regenerable alumina-modified sorbent was developed for CO₂ capture at temperatures below 200 °C. The CO₂ capture capacity of a potassium-based sorbent containing Al₂O₃ (KAlI) decreased during multiple CO₂ sorption (60 °C) and regeneration (200 °C) tests due to the formation of the KAl(CO₃)(OH)₂ phase, which could be converted into the original K₂CO₃ phase above 300 °C. However, the new regenerable potassium-based sorbent (Re-KAl(I)) maintained its CO₂ capture capacity during multiple tests even at a regeneration temperature of 130 °C. In particular, the CO₂ capture capacity of the Re-KAl(I)60 sorbent which was prepared by the impregnation of Al₂O₃ with 60 wt.% K₂CO₃ was about 128 mg CO₂/g sorbent. This excellent CO₂ capture capacity and regeneration property were due to the characteristics of the Re-KAl(I) sorbent producing only a KHCO₃ phase during CO₂ sorption, unlike the KAlI30 sorbent which formed the KHCO₃ and KAl(CO₃)(OH)₂ phases even at 60 °C. This result was explained through the structural effect of the support containing the KAl(CO₃)(OH)₂ phase which was prepared by impregnation of Al₂O₃ with K₂CO₃ in the presence of CO₂.     

Impact of SO2 concentration on the corrosion rate of X70 steel and iron in water-saturated supercritical CO2 mixed with SO2

The corrosion behavior of X70 steel and iron in water-saturated supercritical CO₂ mixed with SO₂ was investigated using weight-loss measurements. As a comparison, the instantaneous corrosion rate in the early stages for iron in the same corrosion environment was measured by resistance relaxation method. Surface analyzes using SEM/EDS, XRD and XPS were applied to study the morphology and chemical composition of the corroded sample surface. Weight-loss method results showed that the corrosion rate of X70 steel samples increased with SO₂ concentration, while the corrosion rate increased before decreasing with SO₂ concentration for iron sample. Comparing resistance relaxation method results with weight-loss method results, it is found that the instantaneous corrosion rate of iron is much higher than the uniform corrosion rate of the iron tablet specimens which are covered with thick corrosion product films after a long period of corrosion. The corrosion product films were mainly composed of FeSO₄ and FeSO₃ hydrates. The possible reaction mechanism under such environment was also analyzed, and the electrochemical reaction between the dissolved SO₂ in the condensed water film with iron is the critical reaction step.     

Direct synthesis of CeO2/SiO2 mesostructured composite materials via sol–gel process

A series of CeO₂/SiO₂ mesostructured composite materials was synthesized by sol–gel process using Pluronic P123 as template, tetraethylorthosilicate as silica source and hexahydrated cerium nitrate as precursor under acid condition. The as-synthesized materials with Ce/Si molar ratio ranging from 0.03 to 0.3 were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), laser Raman spectroscopy (LRS), and N₂ adsorption. Characterization revealed that all samples possess ordered hexagonal mesoporous structure similar to SBA-15 and possess high surface area, large pore volume and uniform pore size. The fact that cerium species are present as highly dispersed CeO₂ nanocrystals in hexagonal matrix was confirmed by XRD combined with high-resolution TEM and selected area electron diffraction (SAED) analysis. Introduction of ceria to silica matrix can cause a distortion of hexagonal ordering structure and decrease pore diameter and increase the wall thickness of mesopores. Moreover, it can be found that this sol–gel route is a feasible, effective and simple method for templating synthesis of CeO₂/SiO₂ composite materials.