Theoretical study of salt effects on the Diels-Alder reaction of cyclopentadiene with methyl vinyl ketone using RISM-SCF theory.

Salt effects on the Diels-Alder reaction of cyclopentadiene with methyl vinyl ketone are investigated using reference interaction site model self-consistent field (RISM-SCF) theory. The rate of the reaction is accelerated by adding LiCl to the water solvent. The structures of four transition states, endo-cis, endo-trans, exo-cis, exo-trans, were found by geometry optimization of the cyclopentadiene and methyl vinyl ketone complexes. The endo-trans structure shows the lowest energy in both water and LiCl solution. The activation barrier of the reaction in LiCl solution is lower than that in water, and the difference is in good agreement with that from experiments. The decrease in the activation barrier arises from destabilization of the reactant species. The salt effect of LiCl makes all species concerning the reaction unstable by the hydrophobic effect; however, the increased hydrophobic effect in the TS complexes is suppressed by making the hydrogen bond, which is stronger compared with the reactant methyl vinyl ketone.

Fate of perfluorooctanesulfonate and perfluorooctanoate in drinking water treatment processes.

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) have been recognized as global environmental pollutants. Although PFOS and PFOA have been detected in tap water from Japan and several other countries, very few studies have examined the fate, especially removal, of perfluorinated compounds (PFCs) in drinking water treatment processes. In this study, we analyzed PFOS and PFOA at every stages of drinking water treatment processes in several water purification plants that employ advanced water treatment technologies. PFOS and PFOA concentrations did not vary considerably in raw water, sand filtered water, settled water, and ozonated water. Sand filtration and ozonation did not have an effect on the removal of PFOS and PFOA in drinking water. PFOS and PFOA were removed effectively by activated carbon that had been used for less than one year. However, activated carbon that had been used for a longer period of time (>1 year) was not effective in removing PFOS and PFOA from water. Variations in the removal ratios of PFOS and PFOA by activated carbon were found between summer and winter months.

Ethylene/polar monomer copolymerization behavior of bis(phenoxy-imine)Ti complexes: formation of polar monomer copolymers.

Bis(phenoxy-imine) Ti complexes bearing a phenyl group ortho to the phenoxy-O can mediate the copolymerization of ethylene and 5-hexene-1-yl-acetate though they are group 4 transition metal catalysts.

Perfluorooctanesulfonate and perfluorooctanoate in raw and treated tap water from Osaka, Japan.

Perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) have been recognized as emerging environmental pollutants because of their ubiquitous occurrence in the environment, biota, and humans. PFOS and PFOA have been detected in water in Japan. Nevertheless, occurrence of PFOS and PFOA in potable water from municipal water treatment plants is not clearly known. We analyzed PFOS and PFOA in raw and tap water samples collected from 14 drinking water treatment plants in winter and summer seasons in Osaka to determine the concentrations of PFOS and PFOA in raw and potable tap water samples. PFOS and PFOA were detected in all raw water samples. Concentration ranges of PFOS and PFOA in raw water were 0.26-22 ng/l and 5.2-92 ng/l, respectively. Whereas the concentrations PFOS in raw water from Osaka were similar to those in other areas in Japan, the concentrations of PFOA were higher than in other areas. Concentration ranges of PFOS and PFOA in potable tap water were 0.16-22 ng/l and 2.3-84 ng/l, respectively. There were positive correlations between PFC concentrations in raw water and tap water samples. Therefore, the removal efficiency of PFCs by the present water treatment may be low. Based on the current action value reported by U.S. Environmental Protection Agency, PFOA concentrations found in tap water in Osaka is not expected to pose health risks.

Titanium and zirconium complexes with non-salicylaldimine-type imine-phenoxy chelate ligands: syntheses, structures, and ethylene-polymerization behavior.

New Ti and Zr complexes that bear imine-phenoxy chelate ligands, [{2,4-di-tBu-6-(RCH=N)-C6H4O}2MCl2] (1: M = Ti, R = Ph; 2: M = Ti, R = C6F5; 3: M = Zr, R = Ph; 4: M = Zr, R = C6F5), were synthesized and investigated as precatalysts for ethylene polymerization. 1H NMR spectroscopy suggests that these complexes exist as mixtures of structural isomers. X-ray crystallographic analysis of the adduct 1HCl reveals that it exists as a zwitterionic complex in which H and Cl are situated in close proximity to one of the imine nitrogen atoms and the central metal, respectively. The X-ray molecular structure also indicates that one imine phenoxy group with the syn C=N configuration functions as a bidentate ligand, whereas the other, of the anti C=N form, acts as a monodentate phenoxy ligand. Although Zr complexes 3 and 4 with methylaluminoxane (MAO) or [Ph3C]+ [B(C6F5)4]-/AliBu3 displayed moderate activity, the Ti congeners 1 and 2, in association with an appropriate activator, catalyzed ethylene polymerization with high efficiency. Upon activation with MAO at 25 degrees C, 2 displayed a very high activity of 19900 (kg PE) (mol Ti)(-1) h(-1), which is comparable to that for [Cp2TiCl2] and [Cp2ZrCl2], although increasing the polymerization temperature did result in a marked decrease in activity. Complex 2 contains a C6F5 group on the imine nitrogen atom and mediated nonliving-type polymerization, unlike the corresponding salicylaldimine-type complex. Conversely, with [Ph3C]+ [B(C6F5)4]-/AliBu3 activation, 1 exhibited enhanced activity as the temperature was increased (25-75 degrees C) and maintained very high activity for 60 min at 75 degrees C (18740 (kg PE) (mol Ti)(-1) h(-1)). 1H NMR spectroscopic studies of the reaction suggest that this thermally robust catalyst system generates an amine-phenoxy complex as the catalytically active species. The combinations 1/[Ph3C]+ [B(C6F5)4]-/AliBu3 and 2/MAO also worked as high-activity catalysts for the copolymerization of ethylene and propylene.

Living copolymerization of ethylene with norbornene catalyzed by bis(pyrrolide-imine) titanium complexes with MAO.

Bis(pyrrolide-imine) Ti complexes in conjunction with methylalumoxane (MAO) were found to work as efficient catalysts for the copolymerization of ethylene and norbornene to afford unique copolymers via an addition-type polymerization mechanism. The catalysts exhibited very high norbornene incorporation, superior to that obtained with Me(2)Si(Me(4)Cp)(N-tert-Bu)TiCl(2) (CGC). The sterically open and highly electrophilic nature of the catalysts is probably responsible for the excellent norbornene incorporation. The catalysts displayed a marked tendency to produce alternating copolymers, which have stereoirregular structures despite the C(2) symmetric nature of the catalysts. The norbornene/ethylene molar ratio in the polymerization medium had a profound influence on the molecular weight distribution of the resulting copolymer. At norbornene/ethylene ratios larger than ca. 1, the catalysts mediated room-temperature living copolymerization of ethylene and norbornene to form high molecular weight monodisperse copolymers (M(n) > 500,000, M(w)/M(n) < 1.20). (13)C NMR spectroscopic analysis of a copolymer, produced under conditions that gave low molecular weight, demonstrated that the copolymerization is initiated by norbornene insertion and that the catalyst mostly exists as a norbornene-last-inserted species under living conditions. Polymerization behavior coupled with DFT calculations suggested that the highly controlled living polymerization stems from the fact that the catalysts possess high affinity and high incorporation ability for norbornene as well as the characteristics of a living ethylene polymerization though under limited conditions (M(n) 225,000, M(w)/M(n) 1.15, 10-s polymerization, 25 degrees C). With the catalyst, unique block copolymers [i.e., poly(ethylene-co-norbornene)(1)-b-poly(ethylene-co-norbornene)(2), PE-b-poly(ethylene-co-norbornene)] were successfully synthesized from ethylene and norbornene. Transmission electron microscopy (TEM) indicated that the PE-b-poly(ethylene-co-norbornene) possesses high potential as a new material consisting of crystalline and amorphous segments which are chemically linked.

FI catalysts: new olefin polymerization catalysts for the creation of value-added polymers.

This contribution reports the discovery and application of phenoxy-imine-based catalysts for olefin polymerization. Ligand-oriented catalyst design research has led to the discovery of remarkably active ethylene polymerization catalysts (FI Catalysts), which are based on electronically flexible phenoxy-imine chelate ligands combined with early transition metals. Upon activation with appropriate cocatalysts, FI Catalysts can exhibit unique polymerization catalysis (e.g., precise control of product molecular weights, highly isospecific and syndiospecific propylene polymerization, regio-irregular polymerization of higher alpha-olefins, highly controlled living polymerization of both ethylene and propylene at elevated temperatures, and precise control over polymer morphology) and thus provide extraordinary opportunities for the syntheses of value-added polymers with distinctive architectural characteristics. Many of the polymers that are available via the use of FI Catalysts were previously inaccessible through other means of polymerization. For example, FI Catalysts can form vinyl-terminated low molecular weight polyethylenes, ultra-high molecular weight amorphous ethylene-propylene copolymers and atactic polypropylenes, highly isotactic and syndiotactic polypropylenes with exceptionally high peak melting temperatures, well-defined and controlled multimodal polyethylenes, and high molecular weight regio-irregular poly(higher alpha-olefin)s. In addition, FI Catalysts combined with MgCl(2)-based compounds can produce polymers that exhibit desirable morphological features (e.g., very high bulk density polyethylenes and highly controlled particle-size polyethylenes) that are difficult to obtain with conventionally supported catalysts. In addition, FI Catalysts are capable of creating a large variety of living-polymerization-based polymers, including terminally functionalized polymers and block copolymers from ethylene, propylene, and higher alpha-olefins. Furthermore, some of the FI Catalysts can furnish living-polymerization-based polymers catalytically by combination with appropriate chain transfer agents. Therefore, the development of FI Catalysts has enabled some crucial advances in the fields of polymerization catalysis and polymer syntheses.

Syndiospecific living propylene polymerization catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands.

The propylene polymerization behavior of a series of Ti complexes featuring fluorine-containing phenoxy-imine chelate ligands is reported. The Ti complexes combined with methylalumoxane (MAO) can be catalysts for living and, at the same time, stereospecific polymerization of propylene at room temperature or above. DFT calculations suggest that the attractive interaction between a fluorine ortho to the imine nitrogen and a beta-hydrogen of a growing polymer chain is responsible for the achievement of room-temperature living propylene polymerization. Although the Ti complexes possess C(2) symmetry, they are capable of producing highly syndiotactic polypropylenes. (13)C NMR is used to demonstrate that the syndiotacticity is governed by a chain-end control mechanism and that the polymerization is initiated exclusively via 1,2-insertion followed by 2,1-insertion as the principal mode of polymerization. (13)C NMR spectroscopy also elucidated that the polypropylenes produced with the Ti complexes possess regio-block structures. Substitutions on the phenoxy-imine ligands have profound effects on catalytic behavior of the Ti complexes. The steric bulk of the substituent ortho to the phenoxy oxygen plays a decisive role in achieving high syndioselectivity for the chain-end controlled polymerization. Over a temperature range of 0-50 degrees C, Ti complex having a trimethylsilyl group ortho to the phenoxy oxygen forms highly syndiotactic, nearly monodisperse polypropylenes (94-90% rr) with extremely high peak melting temperatures (T(m) = 156-149 degrees C). The polymerization behavior of the Ti complexes can be explained well by the recently proposed site-inversion mechanism for the formation of syndiotactic polypropylene by a Ti complex having a pair of fluorine-containing phenoxy-imine ligands.

Living polymerization of ethylene catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands.

Seven titanium complexes bearing fluorine-containing phenoxy-imine chelate ligands, TiCl(2)[eta(2)-1-[C(H)=NR]-2-O-3-(t)Bu-C(6)H(3)](2) [R = 2,3,4,5,6-pentafluorophenyl (1), R = 2,4,6-trifluorophenyl (2), R = 2,6-difluorophenyl (3), R = 2-fluorophenyl (4), R = 3,4,5-trifluorophenyl (5), R = 3,5-difluorophenyl (6), R = 4-fluorophenyl (7)], were synthesized from the lithium salt of the requisite ligand and TiCl(4) in good yields (22%-76%). X-ray analysis revealed that the complexes 1 and 3 adopt a distorted octahedral structure in which the two phenoxy oxygens are situated in the trans-position while the two imine nitrogens and the two chlorine atoms are located cis to one another, the same spatial disposition as that for the corresponding nonfluorinated complex. Although the Ti-O, Ti-N, and Ti-Cl bond distances for complexes 1 and 3 are very similar to those for the nonfluorinated complex, the bond angles between the ligands (e.g., O-Ti-O, N-Ti-N, and Cl-Ti-Cl) and the Ti-N-C-C torsion angles involving the phenyl on the imine nitrogen are different from those for the nonfluorinated complex, as a result of the introduction of fluorine atoms. Complex 1/methylalumoxane (MAO) catalyst system promoted living ethylene polymerization to produce high molecular weight polyethylenes (M(n) > 400 000) with extremely narrow polydispersities (M(w)/M(n) < 1.20). Very high activities (TOF > 20 000 min(-1) atm(-1)) were observed that are comparable to those of Cp(2)ZrCl(2)/MAO at high polymerization temperatures (25, 50 degrees C). Complexes 2-4, which have a fluorine atom adjacent to the imine nitrogen, behaved as living ethylene polymerization catalysts at 50 degrees C, whereas complexes 5-7, possessing no fluorine adjacent to the imine nitrogen, produced polyethylenes having M(w)/M(n) values of ca. 2 with beta-hydrogen transfer as the main termination pathway. These results together with DFT calculations suggested that the presence of a fluorine atom adjacent to the imine nitrogen is a requirement for the high-temperature living polymerization, and the fluorine of the active species for ethylene polymerization interacts with a beta-hydrogen of a polymer chain, resulting in the prevention of beta-hydrogen transfer. This catalyst system was used for the synthesis of a number of unique block copolymers such as polyethylene-b-poly(ethylene-co-propylene) diblock copolymer and polyethylene-b-poly(ethylene-co-propylene)-b-syndiotactic polypropylene triblock copolymer from ethylene and propylene.