Catalyst Residues Research Articles

Functionalized Polyisobutylene and Liquid/Liquid Separations as a Method for Scavenging Transition Metals from Homogeneously Catalyzed Reactions

Ethanedithiol-functionalized polyisobutylene was prepared in one step by a photoinitiated thiol-ene “click” reaction starting from ethanedithiol and polyisobutylene (PIB). The functionalized oligomer product was then used as a soluble sequestrant for transition metals. This PIB-bound thioether-thiol ligand is phase selectively soluble in alkanes and it quantitatively sequesters common transition metals like Cu2+ and Pd2+ into an alkane phase, separating them from polar solvents in a biphasic liquid/liquid separation. The chelating thioether-thiol ligand was also successfully used to remove Cu and Pd transition metal catalyst residues from products in crude reaction mixtures in both azide/alkyne click reactions and cross-coupling reactions using a liquid/liquid extraction. Separation efficiencies exceeding 95% and in many cases 99% were achieved.

Carbon nanotubes catalysis in liquid-phase aerobic oxidation of hydrocarbons: Influence of nanotube impurities

Pure carbon nanotubes (CNTs) have a high electron affinity and as such are able to actively absorb free radicals. This functional feature of CNTs leads to a linear chain breakage with the formation of inert spin adducts and effective inhibition of the oxidation process. However, there is a clear contradiction in this issue in the literature with the analysis of research results indicating that CNTs exhibit antioxidant activity mainly in polymeric materials, under conditions of diffusional restrictions for oxygen access. While, in the liquid-phase oxidation of hydrocarbons by CNTs (CNTs synthesised by the thermal catalytic pyrolysis of carbon-containing raw materials (CVD-process)), the CNTs enhance catalytic processes. In this study the aerobic liquid phase oxidation of cumene and initiated (by azobisisobutyronitrile) at low-temperature (333 K) in the presence of multi-walled carbon nanotubes (MWCNTs) obtained by thermal catalytic pyrolysis of cyclohexane (catalyst-ferrocene) has been undertaken. Kinetic analysis establishes that the catalysis of the oxidation process is associated with the presence of metal compounds in the structure of the MWCNTs. These metals are residues of metal catalysts remaining in the synthesis and in the process of pyrolysis. The metals are converted, as a rule, into metal carbides and are not easily removable by treatment with mineral acids. Thus, in the presence of metals in the composition of MWCNTs, interfering parallel reactions are observed with two processes running in parallel — MWCNTs + R• (RO2 •) → •MWCNTs-R (RO2) and ROOH + M @ MWCNTs → RO• radicals (RO2•). The branching of the chain processes involving hydroperoxides suppresses the route of attachment of alkyl and peroxide radicals to the carbon cage structure of the nanotubes and the reaction proceeds in an autocatalytic mode. Contradictory conclusions regarding the effect of CNTs on the chain processes in the oxidation of organic substances (hydrocarbons, polymers) that exist in the literature are attributed to the lack of control over the presence and nature of the metal containing impurities in the CNTs.

Rapid and selective recovery of palladium from platinum group metals and base metals using a thioamide-modified calix[4]arene extractant in environmentally friendly hydrocarbon fluids

A novel macrocyclic calix[4]arene extractant having a long alkyl chain thioamide, 25,26,27,28-tetrakis(N-n-octylthiocarbamoyl)methoxy-5,11,17,23-tetra-tert-butylcalix[4]arene (1), was synthesized from 25,26,27,28-tetrakis(N-n-octylcarbamoyl)methoxy-5,11,17,23-tetra-tert-butylcalix[4]arene (2) using Lawesson’s reagent. Extractant 1 was characterized using 1H NMR, 13C NMR, FT-IR spectroscopy, and elemental analysis. The Pd(II) extraction abilities of 1 and 2 were studied in high-boiling-point and environmentally friendly hydrocarbon diluents. Pd(II) extraction experiments were conducted using single-metal Pd(II) solutions, simulated mixed palladium group metal (PGM) solutions, and acid-leached automotive catalyst residue solutions. Different experimental conditions, including the shaking time, HCl/HNO3 concentration, Pd(II) concentration, extractant concentration, and the organic/aqueous phase ratio, were studied systematically. Extractant 1 showed very selective (> 99.9%) Pd(II) extraction from the mixed PGM/base metal solutions and the acid-leached automotive catalyst residue solution. Conversely, the Pd(II) extraction ability of extractant 2 was found to be negligible. Extractant 1 showed very fast extraction kinetics and a high extraction capacity as compared to those of the commercial extractant di-n-octyl sulfide. Effective stripping of Pd(II) from 1 was performed using HCI, HNO3, NH3, and HCl-thiourea solutions. Furthermore, 1 was successfully recycled over five extraction/stripping cycles. The Pd(II) extraction mechanism of 1 was studied using FT-IR spectroscopy. Extractant 1 exhibited very selective Pd(II) extraction and high acid stability, demonstrating its industrial applicability for the extraction of Pd(II) from leached automotive catalyst liquors containing PGMs and base metals.

Progress in advanced catalyst and their use in ethylene/propylene copolymerization

Ethylene-propylene rubber (EPR) and ethylene-propylene-diene rubber (EPDM) have important market shares of the industry due to their excellent resistance toward heat, oxidation, weather, and other chemicals. EPR and EPDM have been synthesized by ethylene/propylene copolymerization and ethylene/propylene/nonconjugated diene copolymerization, respectively, employing Ziegler-Natta, metallocene and metal complex catalysts. Catalyst plays important roles in the copolymerization of ethylene and propylene. The progress of Ziegler-Natta, metallocene and metal complex catalysts and their use in ethylene/propylene copolymerization were reviewed. The characteristics and application in the industry of these advanced catalysts were introduced. The effects of metals and their valence in catalysts, chemical structure of ligands, cocatalysts and additives on the catalytic activity, composition, molecular weight, molecular weight distribution and sequence of the resulting ethylene-propylene copolymer were discussed. Vanadium based Ziegler-Natta catalyst is still promising in ethylene/propylene copolymerization. The open active site of vanadium catalyst results in random ethylene-propylene copolymers, which prevent the formation of long crystallized ethylene sequences. Meanwhile, the good solubility in alkanes and low cost of vanadium-based Ziegler-Natta catalyst are benefit for the application for the production of ethylene-propylene rubber in industry. About 70% of the commercial E/P copolymers are conducted by using vanadium based Ziegler-Natta catalysts. However, the unstable active centers brought low activity and the catalyst residues should be removed from the polymer product after deactivation. In order to improve the catalytic activity of vanadium-based Ziegler-Natta catalyst, the additives including electron donor and promoter are usually introduced to the catalytic system. The reactivity ratio of the monomer and the microstructure of the resulting ethylene-propylene copolymer could be adjusted by the additives. Metallocene catalyst, as a single-site catalyst, becomes a promising choice for ethylene/propylene copolymerization because of its high activity, high thermal stability and excellent copolymerization ability. The microstructure of resulting ethylene-propylene copolymer could be controlled by modification of chemical structure of metallocene catalyst. The alternating ethylene-propylene copolymer could be prepared by ethylene/propylene copolymerization using bridged zirconocenes. The half-titanocenes containing monodentate anionic nitrogen ligand exhibit high catalytic activity for ethylene-propylene copolymerization in high reaction temperature. Some of metallocene catalyst such as constrained geometry catalyst and half-titanocene catalyst have been applied in the production of ethylene-propylene rubber. The metal complex catalyst for olefin coordination polymerization and copolymerization have attracted considerable attention. The titanium, zirconium and vanadium complexes exhibit high activity for ethylene/propylene copolymerization and ethylene-propylene copolymers with high and ultra-high molecular weight could be prepared by using these complex catalysts. Living copolymerization of ethylene and propylene is achieved by using titanium complex containing phenoxy-imine ligands. The application in industry for the preparation of ethylene-propylene rubber using complex catalyst is still on the way. In conclusion, the high catalytic activity and propylene incorporation in ethylene/propylene copolymerization could be obtained by using advanced catalysts. In addition, the molecular weight, molecular weight distribution, sequence and topological structure could be controlled by advanced catalysts. Therefore, ethylene-propylene rubber with high performance could be prepared by ethylene-propylene copolymerization using advanced catalysts.

Comparing the pozzolanic activity of aerial lime mortars made with metakaolin and fluid catalytic cracking catalyst residue: A petrographic and physical-mechanical study

We investigated the viability of a fluid catalytic cracking catalyst residue (FC3R) as an alternative sustainable pozzolanic additive in aerial lime mortars. The pozzolanic activity of FC3R was compared to that of metakaolin (MK) by chemical-mineralogical, petrographic and physical investigations. The FC3R showed lower pozzolanic activity than MK when added to aerial lime mortars, owed to the size of FC3R particles that generate less hydrated phases and give place to lower mechanical resistances in mortars. We also demonstrated that FC3R is not a compatible material for use in repair mortars, due to the formation of the harmful soluble salt ettringite.

Discovering Partially Charged Single-Atom Pt for Enhanced Anti-Markovnikov Alkene Hydrosilylation.

The hydrosilylation reaction is one of the largest-scale application of homogeneous catalysis and is widely used to enable the commercial manufacture of silicon products. However, considerable issues including disposable platinum consumption, undesired side reactions and unacceptable catalyst residues still remain. Here, we synthesize a heterogeneous partially charged single-atom platinum supported on anatase TiO2 (Pt1δ+/TiO2) catalyst via an electrostatic-induction ion exchange and two-dimensional confinement strategy, which can catalyze hydrosilylation reaction with almost complete conversion and produce exclusive adduct. Density functional theory calculations reveal that unexpected property of Pt1δ+/TiO2 originates from atomic dispersion of active species and unique partially positive charge Ptδ+ electronic structure that conventional nanocatalysts do not possess. The fabrication of single-atom Pt1δ+/TiO2 catalyst accomplishes a reasonable use of Pt through recycling and maximum atom-utilized efficiency, indicating the potential to achieve a green hydrosilylation industry.

A Comparison Study of Physicochemical Properties and Stabilities of H-Shaped Molecule and the Corresponding Polymer

Rare attention has been paid to the comparison between a monomer and its corresponding polymer in terms of the optoelectronic characteristics. In this article, a model H-shaped molecule and its corresponding polymer, both of which exhibited similar properties including blue emission and solution processing, were designed and synthesized. Optoelectronic properties and various kinds of stability features, including the thermostabilities, spectral stabilities and amplified spontaneous emission characteristic of the monomer and polymer were investigated. In general, the corresponding polymer PH exhibited similar optoelectronic properties but deteriorated stabilities compared with its H-shaped monomer H-1 probably owing to the similar chemical structure but the wider molecular weight distribution and metal catalyst residue. Importantly, monomer H-1 displayed a comparable ASE threshold value with its polymer PH, suggesting that H-shaped fluorene-based small molecules may be more promising optical gain media in solid state amplifers and lasers.

A Ni-based catalyst with polyvinyl pyrrolidone as a dispersant supported in a pretreated fluid catalytic cracking catalyst residue for C9 petroleum resin (C9 PR) hydrogenation

A Ni-based catalyst (Ni-PVP/PFC3R) with polyvinyl pyrrolidone (PVP) as a dispersant supported in a pretreated fluid catalytic cracking catalyst residue (PFC3R) was synthesized and applied to C9 petroleum resin (C9 PR) hydrogenation. For comparison, a Ni catalyst without PVP (Ni/PFC3R) was prepared in the same way. Ni-PVP/PFC3R exhibited higher activity and better stability. The catalysts were characterized by X-ray diffraction, scanning electron microscope, H2-temperature programmed reduction/temperature programmed desorption, Fourier transform infrared spectroscopy and the Brunauer–Emmett–Teller method. The catalysts had a smaller crystallite size and stronger interactions between the Ni species and the PFC3R support in the presence of PVP. The effects of nickel loading, H2 pressure, temperature and reaction time for C9 PR hydrogenation over Ni-PVP/PFC3R were investigated. The bromine number was reduced to 1.25 under the following conditions: nickel content of 12 wt%, PVP amount of 1.5 wt%, temperature of 270°C, H2 pressure of 8 MPa and reaction time of 240 min.

Use of residual diatomaceous earth as a silica source in geopolymer production

The use of binders as an alternative to Portland cement has gained importance in recent years. Among them, geopolymeric binders, developed by the reaction between an aluminosilicate precursor and a high alkalinity solution, have become one of the most promising alternatives. The activating solution generally comprises waterglass and sodium hydroxide. Since waterglass is the most expensive material and has a high environmental impact, using alternative silica sources will lead to more sustainable binders. Previous studies have successfully used rice husk ash (RHA) as a silica source. This research aims to assess the possibility of using diatomaceous earth (or diatomite) as an alternative silica source, like the previous studies with RHA. Diatomite is a sedimentary rock with a high amorphous silica content formed by fossilized diatom remains. In this work, the geopolymer was obtained using a fluid cracking catalyst residue as the precursor and six different activating solution types prepared with commercial products, residual diatomite (from beer and wine industries) and RHA. The results open a new possible route for the reuse and recovery of diatomaceous earth residue, although the compressive strength results of the mortars were slightly lower than those for mortars prepared with RHA or commercial reagents.

Esterification for biodiesel production with a phantom catalyst: Bubble mediated reactive distillation

The initial aim of the paper is to dramatically improve the pretreatment stage of biodiesel production, which converts problematic free fatty acids to fatty acid methyl esters, by introduction of a microbubble mediated reactive distillation stage instead of acid pretreatment. This will shift the conventional esterification process towards completion with a yield higher than 80%, even without high excess methanol. Application of ozone microbubbles has the advantage over acid gas catalysis in that it gives higher conversion and leaves no catalyst residue and requires no further catalyst recovery separation steps (a “phantom” catalyst). Unreacted ozone breaks down into oxygen, so the off-gases are just a humid air stream that can be vented. Importantly, ozonolysis breaks carbon–carbon double bonds into aldehydes and carboxylic acids. Many ester species were found after contacting the feedstock with ozone-rich microbubbles, depending on the molecular structure of the alcohols for the ozonolysis of oleic acid with alcohols, i.e., methanol, ethanol, n-propanol, iso-propanol, and n-butanol. In the case of ozonolysis of used cooking oil mixed with methanol, the results from the GC–MS show that all saturated free fatty acids (including palmitic acid, stearic acid, and myristic acid) are converted to methyl esters within 20 h of 60 °C ozonolysis, whereas trace amounts of these chemicals remain at lower temperatures. The results also show that the conversion of oleic acid to form oleic acid methyl ester is 91.16% after 32 h of ozonolysis at 60 °C. Therefore, the free fatty acid content in used cooking oil is less than 1.33%, which makes it suitable as a reactant for biodiesel production via transesterification. However, this result is different from the result provided by ASTM D974 in that the acid numbers decrease dramatically by 25% at the beginning of ozonolysis followed by a plateau. Moreover, if the fluidic oscillator is used to generate bubbles in ozonolysis of oleic acid mixed with methanol, the results show that the yields of ozonolysis product 1-nonanal increase by 30%. This observation means that ozonolysis of oleic acid is relative to the specific interfacial area, and favoured at low liquid temperatures.

Aqueous electromigration of single-walled carbon nanotubes and co-electromigration with copper ions.

The electromigration behaviour of raw and acid purified single walled carbon nanotubes (SWCNTs) in dilute aqueous systems (0.0034 mg mL-1), in the absence of surfactant, with the addition of either 0.85 M acetic acid or 0.1 M CuSO4, was evaluated using a 2-inch copper cathode and either a 2-inch copper or 0.5-inch platinum anode. The results showed that the electromigration of raw SWCNTs (with a high catalyst residue) in the presence of CuSO4 resulted in the formation of a Cu-SWCNT composite material at the cathode. In contrast, acid purified SWCNTs were observed to diffuse to a copper anode, creating fibrillated agglomerates with "rice-grain"-like morphologies. Upon acidification with acetic acid (or addition of CuSO4) the direction of electromigration reversed towards the cathode as a result of coordination of Cu2+ to the functional groups on the SWCNT overcoming the inherent negative charge of the acid purified SWCNTs. The result was the co-deposition of SWCNTs and Cu metal on the cathode. Addition of 0.005 M EDTA sequesters some of the Cu2+ and resulted in the separation of metal decorated SWCNTs to the cathode and un-decorated SWCNTs to the anode. The resulting SWCNT and Cu/SWCNT deposits were characterized by Raman spectroscopy, XPS, SEM, EDS, and TEM.

Polyurethane foams containing residues of petroleum industry catalysts as recoverable pH-sensitive sorbents for aqueous pesticides

To investigate ways of mitigating the contamination of water with herbicides, which is a well-recognized global problem, we prepared natural resource-based polyurethane foams containing different amounts of petroleum industry catalyst residue (RC) and tested them as atrazine (ATZ, a common herbicide) sorbents in aqueous solutions. The above sorbents were characterized by infrared spectroscopy, electron microscopy, microtomography, thermogravimetric analysis, and X-ray diffraction. The adsorption/desorption of ATZ thereon was investigated as a function of foam composition, pH, initial ATZ concentration, and time. The obtained results showed that the porosity, pore size, and pore interconnectivity of the prepared sorbents were well suited for optimal ATZ removal. At pH 2, foams with high RC contents achieved higher ATZ removal efficiencies (e.g., 25%) than the pristine foam (12%). Conversely, ATZ removal was disfavored at high pH, which was attributed to restricted ATZ–sorbent interactions due to changes in the sorbent surface charge. The presence of other species (such as pectin, which is usually found in fruits) did not interfere with ATZ removal. ATZ desorption was most effective at high pH, enabling the regeneration and re-use of sorbents and thus reducing large-scale application costs.

Reservoir Simulation and Production Optimization of Bitumen/Heavy Oil via Nanocatalytic in Situ Upgrading

This paper presents recent development of in situ upgrading technology (ISUT) for producing heavy oil and bitumen in which a mixture of catalyst, hydrogen, and vacuum residue are injected together with steam to improve oil quality by converting heavy oil components into lighter oil components. Consequently, the produced oil is upgraded and the oil recovery factor is increased while less steam is used, which results in lower capital and operational costs. This technology helps to reduce environmental impacts and greenhouse gas emissions. Numerical simulation of a steam-assisted gravity drainage (SAGD) well pattern was conducted to study the improvement of oil production by applying coinjection of steam and the ISUT mixture (ST-ISUT). The results show that ST-ISUT method can increase the oil recovery factor by 36% and lowers the requirement of steam by 50% in comparison with the conventional steam injection method, and the produced oil has much better quality.

Overcoming Catalyst Residue Inhibition of the Functionalization of Single-Walled Carbon Nanotubes via the Billups–Birch Reduction

The Billups-Birch Reduction chemistry has been shown to functionalize single-walled carbon nanotubes (SWCNTs) without damaging the sidewalls, but has challenges in scalability. Currently published work uses a large mole ratio of Li to carbon atoms in the SWCNT (Li:C) to account for lithium amide formation, however this increases the cost and hazard of the reaction. We report here the systematic understanding of the effect of various parameters on the extent of functionalization using resonant Raman spectroscopy. Addition of 1-iodododecane yielded alkyl-functionalized SWCNTs, which were isolated by solvent extraction and evaporation, and purified by a hydrocarbon wash. The presence of SWCNT growth catalyst residue (Fe) was shown to have a strong adverse effect on SWCNT functionalization. Chlorination-based SWCNT purification reduced the amount of residual Fe, and achieve a maximum ID/IG ratio using a Li:C ratio of 6:1 in a reaction time of 30 min. This result is consistent with published literature requiring 20-fold mole equivalents of Li per mole SWCNT with a reaction time of over 12 h. This new understanding of the factors influencing the functionalization chemistry will help cut down material and process costs, and also increase the selectivity of the reaction toward the desired product.

Geopolymer eco-cellular concrete (GECC) based on fluid catalytic cracking catalyst residue (FCC) with addition of recycled aluminium foil powder

This study presents a new cellular concrete design focused on the energy eco-efficiency and the sustainability concept: geopolymer eco-cellular concrete (GECC). Geopolymer systems made from alkali-activated fluid cracking catalyst residue (FCC) aerated by recycled aluminium foil powders (R) were designed. Commercial aluminium powder (A) was also used as an aerating agent in GECC matrix and its effect was compared with traditional cellular concrete (TCC) made with ordinary Portland cement (OPC). The more alkaline medium of the GECC system improved the hydrogen reaction rate and consequently a higher efficiency in the pore matrix development can be found. Aluminium powder addition of 0.2% by mass of the precursor (FCC) was enough to yield cellular concrete with a natural density significantly lower than that found for TCC. The replacement of A by R made it possible to produce an alternative GECC in which the recycling of the waste aluminium has an important eco-efficiency role because its low cost and its energy saving function. Ground R has less aeration effectiveness than A. However, when co-milling of FCC + R was carried out, advantageous performance GECC was attained. Very interesting properties were obtained for this material: good pore size and its proper distribution in the matrix, low natural density (600–700 kg/m3), relatively high compressive strength (2.5–3.5 MPa), low open/closed porosity ratio (1.15) and the lowest thermal conductivity (0.581 W/mK). This opens an interesting way of reusing both FCC as precursor and aluminium foil waste as an aerating agent in the preparation of new geopolymer eco-cellular concrete (GECC).

Revealing the Cytotoxicity of Residues of Phosphazene Catalysts Used for the Synthesis of Poly(ethylene oxide).

We herein report a case study on the toxicity of residual catalyst in metal-free polymer. Eight-arm star-like poly(ethylene oxide)s were successfully synthesized via phosphazene-catalyzed ring-opening polymerization of ethylene oxide using sucrose as an octahydroxy initiator. The products were subjected to MTT assay using human cancer cell lines (MDA-MB-231 and A2780). Comparison between the crude and purified products clearly revealed that the residual phosphazenium salts were considerably cytotoxic, regardless of the anionic species, and that the cytotoxicity of more bulky t-BuP4 salt was higher than that of t-BuP2 salt. Such results have therefore put forward the necessity for removal of the catalyst residues from PEO-based polymers synthesized through phosphazene catalysis for biorelated applications and for the development of less or nontoxic organocatalysts for such polymers.

Permeation properties of Concrete Added with a Petrochemical Industry Waste

The aim of this study is to evaluate the permeation properties of concrete added with a residue of a petrochemical industry located in Colombia, called catalytic cracking catalyst residue (FCC). Concrete samples with 10, 20 and 30 % of FCC incorporated as cement replacement were evaluated. As reference materials, concrete without addition and concrete added with 20 % of metakaolin (MK) were used. MK is a high performance pozzolan of chemical composition similar to the FCC. The properties studied, in addition to the compressive strength, were: water absorption by total immersion, porosity, surface absorption and capillary sorption. The results showed that the concrete added with FCC and MK had similar behavior, and were slightly higher than the control sample. The total absorption and porosity were below 5 % and 10 % respectively for all samples; this means that the incorporation of the addition reduces the permeability of concrete. In this sense, FCC is considered as a good alternative for producing more durable concrete, being the optimum percentage, 10 % cement replacement.

Screening of additives and other chemicals in polyurethanes by direct analysis in real time mass spectrometry (DART-MS)

Direct analysis in real time mass spectrometry (DART-MS) was used to characterize commercial polyurethane (PUR) samples without sample pretreatment. More than 50 substances, such as catalysts, stabilizers, antioxidants, flame retardants, plasticizers, chain extenders, chain terminators, polyols, solvents, degradation products and contaminants, a few of them presumably toxic, were detected and identified in 18 PUR items. The identification of 16 compounds was further confirmed by DART MS/MS experiments. Catalysts were the largest class of compounds detected in the PURs by DART-MS. In each of the 18 PUR samples, at least one catalyst residue was identified. In addition, DART-MS was able to detect the migration of hazardous chemicals from the PURs to other objects. The collision-induced dissociation (CID) properties of two PUR catalysts, such as the protonated bis[2-(dimethylamino)ethyl] ether (DMAEE) and the protonated 2,2-dimorpholinodiethylether (DMDEE), as well as those of two PUR antioxidants (Antioxidant 1135 and Antioxidant 1076), were explored.

Synthesis of Aliphatic Carbonate Macrodiols and Their Application as Sustainable Feedstock for Polyurethane.

High-molecular-weight poly(propylene carbonate) (PPC) [number-average molecular mass (Mn): 80 000–100 000] is readily alcoholized into PPC macrodiols in the presence of 1,2-propanediol (PDO), 1,4-butanediol (BDO), or 1,6-hexanediol (HDO). The high-molecular-weight PPC and small amount of diols, such as PDO, BDO, or HDO, were stirred at elevated temperatures to convert the extremely viscous high-molecular-weight polymer to low-molecular-weight macrodiols with gel permeation chromatography-measured Mn of about 3000 Da. The chopping reaction of the high-molecular-weight PPC was studied in detail, such as the influences of the catalyst residue, the kinds of alcoholysis agents, reaction temperature, and time. The reaction mechanism of alcoholysis is proposed according to the experimental results. The results indicate that the presence of a trace residue of zinc catalyst (Zn-G-III) in PPC, excess diol feeding, and higher temperature can accelerate the alcoholysis. Moreover, different diols can produce different PPC macrodiols with varying end-capping. Finally, polycarbonate ether urethane can be successfully synthesized using as-synthesized PPC macrodiols and poly(propylene glycol) (Mn ≈ 3000) as the soft segment and 4,4′-diphenylmethane diisocyanate or BDO as the hard segment. The full evaluation for the synthesized PPC macrodiols demonstrates their potential applications in the polyurethane industry.

Selective Growth of Metal-Free Metallic and Semiconducting Single-Wall Carbon Nanotubes.

A major obstacle for the use of single-wall carbon nanotubes (SWCNTs) in electronic devices is their mixture of different types of electrical conductivity that strongly depends on their helical structure. The existence of metal impurities as a residue of a metallic growth catalyst may also lower the performance of SWCNT-based devices. Here, it is shown that by using silicon oxide (SiOx ) nanoparticles as a catalyst, metal-free semiconducting and metallic SWCNTs can be selectively synthesized by the chemical vapor deposition of ethanol. It is found that control over the nanoparticle size and the content of oxygen in the SiOx catalyst plays a key role in the selective growth of SWCNTs. Furthermore, by using the as-grown semiconducting and metallic SWCNTs as the channel material and source/drain electrodes, respectively, all-SWCNT thin-film transistors are fabricated to demonstrate the remarkable potential of these SWCNTs for electronic devices.