Heterogeneous polymer systems. IV. Mechanism of rubber particle formation in rubber-modified vinyl polymers

A mechanism for the formation of rubber particles in the polymerization of solutions of rubber in vinyl monomers is presented. A polymeric oil-in-oil emulsion is formed in the first phase of the polymerization. This polymeric oil-in-oil emulsion is transtormed into a solid dispersion of rubber in vinyl polymer in the second phase of the polymerization. A phase inversion takes place in the emulsion in the first phase of the polymerization. Rubber solution droplets are formed at the phase inversion point. These droplets harden as the polymerization proceeds and are gradually transformed into the solid, crosslinked rubber particles of the final polymer.     

Synthesis of enantiomerically enriched atrolactic acid and other α-hydroxy acids

The α-anions of 2-substituted 1,3-dioxolan-4-ones derived from chiral mandelic and lactic acid ($\text{2a}$, $\text{2b}$; $\text{3a}$; $\text{10a}$, $\text{10b}$) were alkylated with high stereoselectivity. The products formed were hydrolysed to α-hydroxy acids with 65–85% e.e. ((S)(+)-$\text{5}$,$\text{7}$,$\text{9}$, (R)(–)-$\text{13}$).     

Carboxylate and alkyl carbonate coordination at the hydrophobic binding site of redox-active dicobalt amine thiophenolate complexes

A series of new dicobalt complexes of the permethylated macrocyclic hexaamine dithiophenolate ligand H(2)L(Me) have been prepared and investigated in the context of ligand binding and oxidation state changes. The octadentate ligand is an effective dinucleating ligand that supports the formation of bioctahedral complexes with a central N(3)Co(mu-SR)(2)(mu-X)CoN(3) core structure, leaving a free bridging position X for the coordination of the substrates. The acetato- and cinnamato-bridged complexes [(L(Me))Co(II)(2)(mu-O(2)CMe)](+) (2) and [(L(Me))Co(II)(2)(mu-O(2)CCH=CHPh)](+) (5) were prepared by reaction of the mu-Cl complex [(L(Me))Co(II)(2)(mu-Cl)](+) (1) with the corresponding sodium carboxylates in methanol. The electrochemical properties of these and of the methyl carbonate complex [(L(Me))Co(II)(2)(mu-O(2)COMe)](+) (8) were also investigated. All complexes undergo two stepwise oxidations at ca. E(1)(1/2) = +0.22 and at E(2)(1/2) = ca. +0.60 V vs SCE, affording the mixed-valent complexes [(L(Me))Co(II)Co(III)(mu-O(2)CR)](2+) (3, 6, 9) and the fully oxidized Co(III)Co(III) forms [(L(Me))Co(III)(2)(mu-O(2)CR)](3+) (4, 7, 10), respectively. Compounds 3, 6, 9 and 4, 7, 10 refer to acetato-, cinnamato-, and methylcarbonato species, respectively. The Co(II)Co(III) compounds were prepared by comproportionation of the respective Co(II)(2) and Co(III)(2) compounds. The Co(III)Co(III) species were prepared by bromine oxidation of the Co(II)Co(II) forms. The crystal structures of complexes 2.BPh(4).MeCN, 3.(I(3))(2), 5.BPh(4).2MeCN, 6.(ClO(4))(2).EtOH, 7.(ClO(4))(3).MeCN.(H(2)O)(3), and 9.(ClO(4))(2).(MeOH)(2).H(2)O were determined by single-crystal X-ray crystallography at 210 K. The oxidations occur without gross structural changes of the parent complexes. The Co(II)Co(III) complexes are composed of high-spin Co(II) (d(7)) and low-spin Co(III) (d(6)) ions. The Co(III)Co(III) complexes are diamagnetic. The oxidation reactions affect the binding mode of the substrates. In the Co(II)(2) and Co(II)Co(III) forms the carboxylates bridge the two Co(2+) ions in a symmetric mu-1,3 fashion with uniform C-O bond distances, whereas asymmetric bridging modes, with one short C=O and one long C-O distance, are adopted in the fully oxidized species. This is consistent with the observed shifts in vibrational frequencies for nu(as)(C-O) and nu(s)(C-O) across the series.     

Functionalization of single-walled carbon nanotubes with (R-)oxycarbonyl nitrenes

Sidewall functionalization of single-walled carbon nanotubes (SWCNTs) via the addition of (R-)oxycarbonyl nitrenes allows for the covalent binding of a variety of different groups such as alkyl chains, aromatic groups, dendrimers, crown ethers, and oligoethylene glycol units. Such additions lead to a considerable increase in the solubility in organic solvents such as 1,1,2,2-tetrachloroethane (TCE), dimethyl sulfoxide (DMSO), and 1,2-dichlorobenzene (ODCB). The highest solubilities of 1.2 mg/mL were found for SWCNT adducts with nitrenes containing crown ether of oligoethylene glycol moieties in DMSO and TCE, respectively. The presence of chelating donor groups within the addends allowed for the complexation of Cu(2+) and Cd(2+). Atomic force microscopy (AFM) and transmission electron microscopy (TEM) revealed that the functionalized tubes form thin bundles with typical diameters of 10 nm. The presence of thin bundles in solution is supported by (1)H NMR spectroscopy. The elemental composition of the functionalized SWCNT was determined by X-ray photoelectron spectroscopy (XPS). The use of Raman and electron absorption spectroscopy (UV/Vis-nIR) showed that the electronic properties of the SWCNTs are mostly retained after functionalization, indicating a low degree of addition within this series of SWCNT derivatives.     

Global uniqueness for an inverse boundary problem arising in elasticity

Summary We prove that we can determine the Lamé parameters of an elastic, isotropic, inhomogeneous medium in dimensionsn3, by making measurements of the displacements and corresponding stresses at the boundary of the medium.Oblatum 14-VI-1993 & 22-XII-1993Partially supported by NSF Grant DMS-9100178 and ONR grant N 0014-93-1-0295     

Segregation of inorganic ions at surfaces of polar nonaqueous liquids.

We present a short review of recent computational and experimental studies on surfaces of solutions of inorganic salts in polar nonaqueous solvents. These investigations complement our knowledge of aqueous interfaces and show that liquids such as formamide, liquid ammonia, and ethylene glycol can also surface-segregate large polarizable anions like iodide, albeit less efficiently than water. For liquids whose surfaces are covered with hydrophobic groups (e.g. methanol), the surface-ion effect all but disappears. Based on the present data a general picture of inorganic-ion solvation at the solution-vapor interface of polar liquids is outlined.     

EPMA Investigation of Roman Coin Silvering Techniques

Ancient Roman silver coins, especially forgeries, contain various amounts of silver on the surfaces. The state of preservation of the outer layer can vary strongly among different areas of the same coin, thus an investigation of the entire surface is indispensable. The measurement of the silver distribution is a first step towards uncovering the manufacturing techniques. Element mapping by electron probe micro-analysis (EPMA) with increasing step size allows a survey of the complete coin surface. The suitability of this approach is shown and applied to coins having a dark optical appearance and unknown minting technique.