Polymerization of ethylene with supported zirconium organic compounds

The polymerization of ethylene was studied with supported catalysts prepared by the reaction of Zr(benzyl)₄ and Al₂O₃. The influence of the preparation of the catalysts and the reaction conditions on the overall rate of the polymerization was established. The rate exhibits a maximum which depends on the thermal pretreatment of the support and the quantity of the fixed Zr(benzyl)₄. The concentration of the active centres of the catalysts was determined by quenching the polymerization with labelled butanol. The catalysts possess active centres which have different rates of propagation for ethylene. The decrease of the polymerization rate is caused by chemical reaction. The higher the concentration of free hydroxyl groups on the catalyst, the higher the rate of deactivation. Hydrogen in the monomer feed produces a decrease or an increase of the polymerization rate depending on the preparation of the catalysts.     

Polymerization of ethylene oxide by alkali metal-naphthalene complexes in tetrahydrofuran

The kinetics of ethylene oxide polymerization in THF, with Na, K and Cs-naphthalene complexes as initiators, have been studied in detail.     

Polymerization with organoboron compounds

In the presence of organoboron compounds, free-radical polymerization of vinyl monomers can proceed in spite of the presence of excess of typical radical inhibitors. The concept of free radical–organoboron complex formation is introduced to explain the unique role of organoboron compounds in such a polymerization system.     

Surface properties of inclusion complexes between alpha-cyclodextrin and poly(ethylene oxide)

The surface properties of the supramolecular inclusion complex (IC) obtained from the threading of alpha-cyclodextrin (alpha-CD) onto poly(ethylene oxide) (PEO) free in solution are studied. The complexes were characterized by IR, (1)H NMR spectroscopy, and thermal analysis. The variation of the interfacial tension, gamma(int), with inclusion complex (IC) concentration and temperature were determined. The results were compared with those found for PEO under the same conditions. alpha-CD does not present surface activity. To quantify the adsorption process of IC and PEO in aqueous medium, the Gibbs equation was used. The driving force for adsorption of IC at the air/aqueous interface seems to arise from an enthalpic contribution. The wettability of the alpha-CD, PEO, and IC films with two liquids was determined by static contact angle measurements. The hydrophobicity degree was estimated. IC is more hydrophobic than PEO and alpha-CD.     

Poly[(methylene oxide) oligo(ethylene oxide)] vs. poly(ethylene oxide) as hosts for neodymium compounds

In view of the residual crystallinity in PEO found to limit the solubility of some Nd³⁺-compounds, amorphous PEO (aPEO) was synthesized for exploration as an alternative host. Complexation, solubility limit, morphology, and response to moisture absorption in the doped systems were investigated using FTIR, DSC, TGA, and WAXD techniques. Representing a perturbation to the structural regularity present in PEO, aPEO was found to present lower solubilities for dopants (Nd(act)₃ and Nd(acac)₃, both characterized by a weak Nd³⁺–ether oxygen interaction. On the other hand, no difference in solubility was observed for dopant Nd(NO₃)₃, characterized by a strong Nd³⁺–ether oxygen interaction. Laser interferometry was employed to assess film homogeneity of the Nd(NO₃)₃-doped systems across a 20-mm diameter, and the measured peak-to-valley distortion values were observed to be encouraging for practical applications. © 1994 John Wiley & Sons, Inc.     

Reaction of alkenyldichlorophosphines with ethylene oxide and ethylene sulfide

Conclusions In contrast to ethylane oxide, ethylene sulfide reacts with the styryl- and isobutenyldichlorophosphines only in the presence of catalysts. The course of the discussed reactions is facilitated by solvents with a high electron-donor capacity. The obtained results are discussed from the standpoint of primary donor-acceptor interactions of the reactants.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 457–461, February, 1976.     

Hydrate inclusion compounds

There are three general classes of hydrate inclusion compounds: the gas hydrates, the per-alkyl onium salt hydrates, and the alkylamine hydrates. The first are clathrates, the second are ionic inclusion compounds, the third are semi-clathrates. Crystallization occurs because the H₂O molecules, like SiO₂, can form three-dimensional four-connected nets. With water alone, these are the ices. In the inclusion hydrates, nets with larger voids are stabilized by including other guest molecules. Anions and hydrogen-bonding functional groups can replace water molecules in these nets, in which case the guest species are cations or hydrophobic moieties of organic molecules. The guest must satisfy two criteria. One is dimensional, to ensure a comfortable fit within the voids. The other is functional. The guest molecules cannot have either a single strong hydrogen-bonding group, such as an amide or a carboxylate, or a number of moderately strong hydrogen-bonding groups, as in a polyol or a carbohydrate.The common topological feature of these nets is the pentagonal dodecahedra: i.e., 5¹²-hedron. These are combined with 5¹²6²-hedra, 5¹²6³-hedra, 5¹²6⁴-hedra and combinations of these polyhedra, to from five known nets. Two of these are the well-known 12 and 17 Å cubic gas hydrate structures,Pm3n, Fd3m; one is tetragonal,P4 ₂/mnm, and two are hexagonal,P6 ₃/mmc andP6/mmm. The clathrate hydrates provide examples of the two cubic and the tetragonal structures. The alkyl onium salt hydrates have distorted versions of thePm3n cubic, the tetragonal, and one of the hexagonal structures. The alkylamine hydrate structures hitherto determined provide examples of distorted versions of the two hexagonal structures.There are also three hydrate inclusion structures, represented by single examples, which do not involve the 5¹²-hedra. These are 4(CH₃)₃CHNH₂·39H₂O which is a clathrate; HPF₆·6H₂O and (CH₃)₄NOH·5H₂O which are ionic-water inclusion hydrates. In the monoclinic 6(CH₃CH₂CH₂NH₂)·105H₂O and the orthorhombic 3(CH₂CH₂)₂NH·26H₂O, the water structure is more complex. The idealization of these nets in terms of the close-packing of semi-regular polyhedra becomes difficult and artificial. There is an approach towards the complexity of the water salt structures found in the crystals of proteins.     

Phase diagrams with nonstoichiometric intermediate inclusion compounds

A model was presented for the p–T diagram of a binary system comprising a polymer and a highly volatile component in which there are intermediate nonstoichiometric phases. The most characteristic polythermal and polybaric sections of the spatial p–T–x diagram are considered.     

In-situ characterization of self-assembled monolayers of water-soluble oligo(ethylene oxide) compounds

In-situ spectroscopic ellipsometry (SE) was utilized to examine the formation of the self-assembled monolayers (SAMs) of the water-soluble oligo(ethylene oxide) [OEO] disulfide [S(CH(2)CH(2)O)(6)CH(3)](2) {[S(EO)(6)](2)} and two analogous thiols - HS(CH(2)CH(2)O)(6)CH(3) {(EO)(6)} and HS(CH(2))(3)O(CH(2)CH(2)O)(5)CH(3) {C(3)(EO)(5)} - on Au from aqueous solutions. Kinetic data for all compounds follow simple Langmuirian models with the disulfide reaching a self-limiting final state (d=1.2nm) more rapidly than the full coverage final states of the thiol analogs (d=2.0nm). The in-situ ellipsometric thicknesses of all compounds were found to be nearly identical to earlier ex-situ ellipsometric measurements suggesting similar surface coverages and structural models in air and under water. Exposure to bovine serum albumin (BSA) shows the self-limiting (d=1.2nm) [S(EO)(6)](2) SAMs to be the most highly protein resistant surfaces relative to bare Au and completely-formed SAMs of the two analogous thiols and octadecanethiol (ODT). When challenged with up to near physiological levels of BSA (2.5mg/mL), protein adsorption on the final state [S(EO)(6)](2) SAM was only 3% of that which adsorbed to the bare Au and ODT SAMs.     

Morphology and Crystalline Structure of Inclusion Compounds Formed between Poly（ethylene glycol） and Urea

The poly（ethylene glycol） （PEG, with Mw 2000）-urea inclusion compound （IC） crystallized at high temperature region showed two typical orientations, flat-on and edge-on crystals. 2D-XRD and polarized FTIR spectroscopy revealed that the PEG chains within urea channels were perpendicular to the substrate in fiat-on oriented crystals, while PEG chain axes were parallel to the substrate and lay along the growth direction in the edge-on crystals. FT1R absorption bands of PEG in the ICs are sensitive to orientation of the crystals. A scheme of PEG chain packing in the urea IC channel was proposed, which could explain the orientation of the crystal nucleus causing the two types of morphologies. Furthermore, functioning of PEG2000 chain end with analine had significantly influence on the morphology and orientation of the inclusion compound crystals, due to the defects caused by large terminal groups included in the urea channel.     

Polymerization of ethylene oxide with a calixarene‐based precursor: Synthesis of eight‐arm poly(ethylene oxide) stars by the core‐first methodology

Eight‐arm poly(ethylene oxide) (PEO) stars were prepared by the core‐first method with a newly designed octahydroxylated precursor. This compound was readily obtained in two steps from commercially available tert‐butylcalix[8]arene. The choice of the proper solvent of polymerization proved crucial to obtain PEO star materials with a narrow distribution of molar masses. For instance, the use of dimethyl sulfoxide (DMSO) resulted in PEO samples of rather large polydispersities (PDI: 1.3–1.5). In this solvent, the calixarene‐based precursor was only sparingly soluble, and an attempt to metalate its eight hydroxyl groups produced insoluble alkoxides. In addition, the presence of a side population of low‐molar‐mass species attributable to linear chains was detected because of the chain transfer of propagating alkoxides to DMSO. Polymerization experiments carried out in tetrahydrofuran (THF) as solvent afforded better control over the molar masses and PDIs. This was related to the better solubility of the octafunctional calixarene‐based precursor in THF and to the small tendency of the alkoxides formed to aggregate in that solvent. Under such conditions, all eight hydroxyl functions efficiently initiated the polymerization of ethylene oxide. In this way, well‐defined PEO stars (PDI < 1.2) of tunable molar masses incorporating a calixarene‐based core could be obtained, as it was supported by the characterization of the samples by size exclusion chromatography, NMR, and viscometry. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1669–1676, 2003     

Reaction of ethylene oxide with methyl isothiocyanate

Summary When ethylene oxide reacts with methyl isothiocyanate in the presence of tetraethylammonium bromide, basically a compound of the spiran type (I) is obtained; thermal decomposition of this compound results in the formation of the trimethyl ester of dithioisocyanuric acid and ethylene sulfide.     

Reactions of actinide ions with ethylene oxide

Naked and oxo-ligated actinide (An) monopositive ions were reacted with ethylene oxide, cyclo-C(2)H(4)O (EtO). Along with An = U, Np, Pu and Am, ions of two lanthanide (Ln) elements, Ln = Tb and Tm, were studied for comparison. Metal and metal oxide ions, M(+), MO(+) and MO(2)(+), were generated by laser ablation and immediately reacted with EtO. Unreacted and product ions were detected by time-of-flight mass spectrometry. It was apparent that the overall reaction cross-sections decreased in the order U(+) > or = Np(+) > Pu(+) > Am(+). A primary reaction channel for each studied metal was the formation of MO(+) from M(+), in accord with the expected exothermicity of oxygen abstraction from EtO. For U, Np and Pu, the dioxides were also major products, indicating OAn(+)--O dissociation energies of at least 350 kJ mol(-1), the energy required for O-atom abstraction from EtO. For Am, Tb and Tm, the dioxides were only very minor products, reflecting the stabilities of the trivalent states and resistance to oxidation to higher valence states; the structures/bonding in these MO(2)(+) are intriguing given that the formal pentavalent bonding state is effectively unattainable. It was demonstrated that EtO, unlike more thermochemically favorable but kinetically restricted O-donors, is effective at achieving facile oxidation of actinide metal ions to the monoxide, and to the dioxide if the second O-abstraction reaction is exothermic. Several intriguing minor products were also identified, most of which incorporate metal--oxygen bonding and are attributed to the oxophilicity of the f-block elements; the contrast to the behavior of first-row d-block transition elements is striking in this regard. Particularly noteworthy was the formation of MH(4)(+) (and MOH(4)(+)), evidently via abstraction of all four H atoms from a single C(2)H(4)O molecule; the structures/bonding in these novel 'hydride' species are indeterminate and warrant further attention.