Copper octanoate

Starting Materials. Polyethylene, low density (0.92), was obtained from Union Carbide as additive-free pellets. Copper propionate, used only for liquid-phase solubilities, was obtained commercially and used without further purification. All other copper salts were synthesized as follows equal equivalents of Cu(OH)2 CuC03 ( 99+%, ROC/RIC Chemical Corp.) and the appropriate carboxylic acid were stirred in a minimum amount of xylene and heated to 120°C under N2 overnight. After reacting the xylene solution was diluted with additional xylene, reheated, and filtered hot to remove any copper oxides and/or carbonates. The xylene solution was cooled and the resultant precipitate collected by suction filtration and washed with additional xylene and then hexane. Additional recrystallization was done from hexane, isooctane, and/or xylene. In the case of the copper octanoate the solubility in xylene was quite high, so minimum amounts were used and recrystallization was done from hexane. Analyses for copper Cu(C7Hi5C02)2,... 

The normal plot of the effects (Fig. 4A.9) is very easy to interpret, and shows that gel time is totally controlled by three factors (5 = dimethylaniline, 4 = copper octanoate and 1 = hydroquinone, in this order of importance). Factors 4 and 5 contribute to lower the gel time, whereas factor 1 tends to increase it. There is no evidence of significant interactions. This is welcome, because it means the factors can be varied independently of one another, at the customer s convenience. The numerical values on the right side of the plot are the cumulative probabilities corresponding to the z values on the left. 

Polysiloxanes with terminal hexenyl groups were converted by ozonol-ysis into polysiloxanes with terminal aldehyde functionality. These were used in combination with copper octanoate, triethylamine, pyridine and triphenylphosphine to initiate the polymerization of styrene, methyl methacrylate and styrene/methyl methacrylate mixtures at 70°C. The polymerizations yielded block copolymers containing polysiloxane and vinyl (co)polymer segments. Depending on how the polymerizations terminated, the block copolymers had triblock or multiblock architectures. 

Polymerization Procedure. All polymerizations were conducted in one ounce bottles under an argon atmosphere either in bulk or using benzene as a solvent to minimize chain transfer reactions. A typical reaction mixture contained 10 ml benzene that had been distilled from CaH2, copper octanoate (0.1 g, 2.86 x lO mole), pyridine (0.5g), triphenylphosphine (0.3g, 1.14 x 10 mole), triethylamine (O.lg, 1 x 10 mole), monomer (- 5 ml) and aldehyde-functional polydimethylsiloxane (0.4 - 2.34 g, 3.1 x lO" mole of aldehyde groups). After being heated at 70 C for 21 hr., the reaction mixtures were cooled to room temperature, diluted with benzene, and added to methanol to pre-... 

When solutions of aldehyde-functional polysiloxanes, copper octanoate, trieth-ylamine, pyridine, triphenylphosphine and monomer in inert solvents such as benzene are heated, radicals can be generated at the polysiloxane ends and these can initiate polymerization. This is shown below, where M is a monomer unit. 

Table II provides information about styrene polymerizations that were initiated by polymers I, II, and III in combination with copper octanoate, GjP, EtjN and pyri-...

An alternative route for the synthesis of TV-methyl amino acids without racemization is shown in Scheme 8.[98 This method includes the use of TBPB in the presence of copper(I) octanoate. The proposed mechanism of this free radical reaction is given in Scheme 8. Electron transfer from copper(I) to TBPB affords the copper(II), benzoate, and tBuO radical 4, which undergoes (3-scission to acetone and methyl radical 5. In turn, electron transfer from the urethane to the copper(II) ion, followed by proton transfer, affords the corresponding urethane radical 6, which reacts with the methyl radical 5 to give the desired product in overall yields of 54% (Z derivative) or 57% (Boc derivative), respectively. 

Benzoyloxylation of p-lactams.1 Reaction of p-lactams with this reagent in the presence of copper(II) octanoate effects benzoyloxylation at C4, a to the nitrogen when the nitrogen is substituted by a phenyl or /-butyl group. However, reaction at an exocyclic carbon a to the nitrogen is a competing reaction when possible. 

Copper(II) octanoate, 58 Dibromomethane-Zinc-Copper(I) chloride, 93... 

The carbene generated by copper-catalyzed decomposition of diazoketone 283 adds intramolecularly to the aromatic carbon-carbon bond of the phenoxy group, affording a norcaradiene derivative that then ring-opens to produce a cycloheptatriene framework fused to the y-lactone in 284 (86T4319). Rhodium(II) octanoate-catalyzed decomposition of 3,4-... 

Effect of Various Additives. From the results mentioned above, it is evident that the copper stearate is converted to inhibitors by the interactions of oxidation products, and the oxygen uptake appears to level oflF after a certain time. Thus, the effects of model compounds of oxidation products (n-octylaldehyde, n-octanoic acid, 2-octanone, n-octanol, and n-octanoic aCid methyl ester), tert-hutyl hydroperoxide, and di-ter -butyl peroxide on the thermal oxidation of the polypropylene in trichlorobenzene were examined. 

The effects of model compounds of oxidation products on the oxidation of the polymer in trichlorobenzene were examined. As a typical example of the oxygenated model compounds, the effect of small amounts of n-octanoic acid (5 X 10 3M, 1 X 10 2M, 2 X 10 2M) on the oxidation of the polymer in the presence of the copper stearate is shown in Figure 13. The effects of all model compounds of oxidation products are sum-... 

Solubilities. Extrapolation from Liquid Phase. Solubilities of various copper carboxylate salts in pure octane and hexadecane at 90 °C are shown in Figure 2. The solubility of the octanoate salt is quite high but cannot be measured accurately because of experimental difficulties (discussed above). If one applies regular solution theory (6) with the assumption that the excess free energies of mixing (or alternatively the solvent-solute interaction parameters) are equal for a particular salt in an alkane medium, then the following equation can be derived (7) ... 

Soap, metaiiic n. Any product derived by reacting a fatty acid with a metal. Metallic soaps are widely used as stabilizers for plastics. The fatty acids commonly used are lauric, stearic, ricinoleic, naphthenic, octanoic (2-ethylhexanoic), rosin, and tall oil. Typical metals are aluminum, barium, calcium, cadmium, copper, iron, lead, magnesium, tin, and zinc. 

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