Silver catalysts polymers

Direct Oxidation of Propylene to Propylene Oxide. Comparison of ethylene (qv) and propylene gas-phase oxidation on supported silver and silver—gold catalysts shows propylene oxide formation to be 17 times slower than ethylene oxide (qv) formation and the CO2 formation in the propylene system to be six times faster, accounting for the lower selectivity to propylene oxide than for ethylene oxide. Increasing gold content in the catalyst results in increasing acrolein selectivity (198). In propylene oxidation a polymer forms on the catalyst surface that is oxidized to CO2 (199—201). Studies of propylene oxide oxidation to CO2 on a silver catalyst showed a rate oscillation, presumably owing to polymerization on the catalyst surface upon subsequent oxidation (202). 

The comparison of more complete kinetic equations (242) and (243) with experimentation is hampered by the instability of activity of silver catalysts (59). The effects arising from the penetration of oxygen into the subsurface silver layer (63) and the formation of a polymer film on the surface (70), an extremely high sensitivity of the catalyst to the traces of compounds of such elements as S and Cl that may be present in the reactants as impurities, can be the sources of this instability. 

Trilialophenols can be converted to poly(dihaloph.enylene oxide)s by a reaction that resembles radical-initiated displacement polymerization. In one procedure, either a copper or silver complex of the phenol is heated to produce a branched product (50). In another procedure, a catalytic quantity of an oxidizing agent and the dry sodium salt in dimethyl sulfoxide produces linear poly(2,6-dichloro-l,4-polyphenylene oxide) (51). The polymer can also be prepared by direct oxidation with a copper—amine catalyst, although branching in the ortho positions is indicated by chlorine analyses (52). 

Catalysts. Silver and silver compounds are widely used in research and industry as catalysts for oxidation, reduction, and polymerization reactions. Silver nitrate has been reported as a catalyst for the preparation of propylene oxide (qv) from propylene (qv) (58), and silver acetate has been reported as being a suitable catalyst for the production of ethylene oxide (qv) from ethylene (qv) (59). The solubiUty of silver perchlorate in organic solvents makes it a possible catalyst for polymerization reactions, such as the production of butyl acrylate polymers in dimethylformamide (60) or the polymerization of methacrylamide (61). Similarly, the solubiUty of silver tetrafiuoroborate in organic solvents has enhanced its use in the synthesis of 3-pyrrolines by the cyclization of aHenic amines (62). 

Chemical reduction is used extensively nowadays for the deposition of nickel or copper as the first stage in the electroplating of plastics. The most widely used plastic as a basis for electroplating is acrylonitrile-butadiene-styrene co-polymer (ABS). Immersion of the plastic in a chromic acid-sulphuric acid mixture causes the butadiene particles to be attacked and oxidised, whilst making the material hydrophilic at the same time. The activation process which follows is necessary to enable the subsequent electroless nickel or copper to be deposited, since this will only take place in the presence of certain catalytic metals (especially silver and palladium), which are adsorbed on to the surface of the plastic. The adsorbed metallic film is produced by a prior immersion in a stannous chloride solution, which reduces the palladium or silver ions to the metallic state. The solutions mostly employed are acid palladium chloride or ammoniacal silver nitrate. The etched plastic can also be immersed first in acidified palladium chloride and then in an alkylamine borane, which likewise form metallic palladium catalytic nuclei. Colloidal copper catalysts are of some interest, as they are cheaper and are also claimed to promote better coverage of electroless copper. 

Ethylene oxide, the simplest epoxide, is an intermediate in the manufacture of both ethylene glycol, used for automobile antifreeze, and polyester polymers. More than 4 million tons of ethylene oxide is produced each year in the United States by air oxidation of ethylene over a silver oxide catalyst at 300 °C. This process is not useful for other epoxides, however, and is of little value in the laboratory. Note that the name ethylene oxide is not a systematic one because the -ene ending implies the presence of a double bond in the molecule. The name is frequently used, however, because ethylene oxide is derived pom ethylene by addition of an oxygen atom. Other simple epoxides are named similarly. The systematic name for ethylene oxide is 1,2-epoxyethane. 

A number of modified reaction conditions have been developed. One involves addition of silver salts, which activate the halide toward displacement.94 Use of sodium bicarbonate or sodium carbonate in the presence of a phase-transfer catalyst permits especially mild conditions to be used for many systems.95 Tetraalkylammonium salts often accelerate reaction.96 Solid-phase catalysts in which the palladium is complexed by polymer-bound phosphine groups have also been developed.97 Aryl chlorides are not very reactive under normal Heck reaction conditions, but reaction can be achieved by inclusion of triphenylphosphonium salts with Pd(OAc)2 or PdCl2 as the catalyst.98... 

MSA and other lower alkanesulfonic acids are useful for plating of lead, nickel, cadmium, silver, and zinc (409). MSA also finds use in plating of tin, copper, lead, and other metals. It is also used in printed circuit board manufacture. In metal finishing the metal coating can be stripped chemically or electrolytically with MSA. MSA also finds use in polymers and as a polymer solvent and as a catalyst for polymerization of monomers such as acrylonitrile. MSA also finds use in ion-exchange resin regeneration because of the high solubility of many metal salts in aqueous solutions. 

Limited structural information is available for silver(I) carboxylates, despite their extensive use as catalysts in the manufacture of urethane polymers. This is in part due to their frequent insoluble and light-sensitive nature making chemical characterization of the complexes difficult. Dimeric structures have been reported for the perfluorobutyrate249 and trifluoroacetate complexes.250 In each case two-fold symmetry was crystallographically imposed. The Ag—O bond lengths were 223-224 pm, and in the more accurate determination of the trifluoroacetate, the Ag—Ag separation was found to be 297 pm. A dimeric structure was also found for the silver(I) complex of 3-hydroxy-4-phenyl-2,2,3-trimethylhexane carboxylate.251 In the asymmetric crystal unit the Ag---Ag separations were 277.8 and 283.4 pm. 

Complexation of the three silver salts Ag(CBnH12), Ag(CBnH6Br6), and Ag(OTf) to polymer bound triphenylphosphine also yielded active catalyst systems. The polymer-bound catalyst could be recycled 3 times with no loss of activity. Dimeric complexes [e.g., [Ag(PPh3)2(CBnH12)]2] were significantly poorer catalysts. 

There is evidence for isomerization of chemisorbed propylene oxide to acrolein on silver and for surface polymer formation on metal oxide catalysts (11,12). Formation of a surface polymeric structure has also been observed during propylene oxidation on silver (13). It appears likely that the rate oscillations are related to the ability of chemisorbed propylene oxide to form relatively stable polymeric structures. Thus chemisorbed monomer could account for the steady state kinetics discussed above whereas the superimposed fluctuations on the rate could originate from periodic formation and combustion of surface polymeric residues. 

Silicones, 5,113-114,135-136,261 Silk, 33-34,47, 61, 66,171 Silly Putty, 125-126,262 Silver Spencer 129 Silver halide, 122 Single-site catalysts, 106-107 Smart materials, 206-209, 218 for food packaging, 206-207 for military applications, 208 sensors for, 207,208 shape-memory polymers, 207-208 Society of Automotive Engineers (SAE), 121 Sodium acrylate, 122 ... 

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