Ethylene - Carbon Monoxide

Kiji and co-workers [87] investigated the composition and microstructure of alternating olefin-carbon monoxide copolymers and their derivatives including ethylene-styrene-carbon monoxide alternating polymer, norbornene-amine copolymer and polymers modified with phosphorus pentasulfide or phosphorus pentoxide or primary amines. 

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Norrish type I chemistry is claimed to be responsible for about 15% of the chain scission of ethylene—carbon monoxide polymers at room temperature, whereas at 120°C it promotes 59% of the degradation. Norrish I reactions are independent of temperature and oxygen concentration at temperatures above the T of the polymer (50). 

Quantum, by contrast, converted an ethylene—carbon monoxide polymer into a polyester-containing terpolymer by treatment with acidic hydrogen peroxide, the Baeyer-Villiger reaction (eq. 11). Depending on the degree of conversion to polyester, the polymer is totally or partially degraded by a biological mechanism. 

Other patents include copolymers of vinyl ketones with acrylates, methacrylates, and styrene (53) an ethylene—carbon monoxide (1—7 wt %) blend... 

With Unsaturated Compounds. The reaction of unsaturated organic compounds with carbon monoxide and molecules containing an active hydrogen atom leads to a variety of interesting organic products. The hydroformylation reaction is the most important member of this class of reactions. When the hydroformylation reaction of ethylene takes place in an aqueous medium, diethyl ketone [96-22-0] is obtained as the principal product instead of propionaldehyde [123-38-6] (59). Ethylene, carbon monoxide, and water also yield propionic acid [79-09-4] under mild conditions (448—468 K and 3—7 MPa or 30—70 atm) using cobalt or rhodium catalysts containing bromide or iodide (60,61). 

Random ethylene-carbon monoxide copolymers have been known for many years and have properties somewhat similar to low density polyethylene. Alternating ECO copolymers were first produced long ago by Reppe of BASF in... 

Photodegradation may involve use of inherently photo-unstable polymers or the use of photodegradant additives. An example of the former are ethylene-carbon monoxide polymers in which absorption of light by the ketone group leads to chain scission. The polymer becomes brittle and forms a powder. Such materials are marketed by Dow and by Du Pont. Other examples are the copolymers of divinyl ketone with ethylene, propylene or styrene marketed by Eco Atlantic. 

The blending of polymeric organic carbonyl compounds, e.g., ethylene/carbon monoxide copolymer, with the parent polymer, e.g., polyethylene, gives a plastic film material that degrades within 3 months. 

Ethylene carbonate, 10 640, 665 in lithium cells, 3 459 molecular formula, 6 305t physical properties, 6 306t transesterification of, 13 651-652 Ethylene-carbon monoxide (ethylene-CO) copolymers, 5 9 10 197 Ethylene chlorohydrin process, 10 640 Ethylene-chlorotrifluoroethylene (E-CTFE) alternating copolymer (ECTFE), 15 248... 

A route not yet commercialized is the reaction of ethylene, carbon monoxide, and air to give AA. The ethylene is dissolved in acetic acid. The process talces place at 270°F and 1100 psi in the presence of palladium chloride-copper chloride catalyst. Yields are 80—85%. If the by-product and corrosion problems can be licked, the process will probably catch on. 

Propionic Acid. The Reppe reaction is used to transform ethylene, carbon monoxide, and water to propionic acid.82 [Ni(CO)4] is formed in situ from nickel salts under reaction conditions (270-320°C, 200-240 atm). The addition of halogens and phosphine ligands allows milder reaction conditions (Halcon process, 170-225°C, 10-35 atm). Propionic acid yields are around 95%. 

With respect to the untreated Reactor I, the hydrogen peroxide yield was very small, and that of methane, ethylene, carbon monoxide, and acetaldehyde was large. The small ratio of hydrogen peroxide to propylene is possibly caused by the successive decomposition of hydrogen peroxide once formed. With aged Reactor II, the yield of hydrogen peroxide and methanol increased, while that of methane, ethylene, and carbon monoxide decreased significantly. 

Effect of other factors on cellulose. Dry distillation at a temperature above 150°C causes cellulose to produce compounds of low molecular weight, such as water, methane, ethylene, carbon monoxide, carbon dioxide, acetic acid, and acetone. According to Pictet [49] dry distillation under reduced pressure yields a substance having the empirical formula C6H10Oj, laevo-glucosan which probably is /3-D-glucopyranose anhydride ... 

Chatani, Y., T. Tazikawa, S. Mcrahashi, Y. Sakata, and Y. Nishimura Crystal structure of polyketone (1 1 ethylene/carbon monoxide) copolymer. J. Polymer Sci. 55, 811 (1961). 

Furans have also been incorporated (76USP3979367) into the main chains of polymers by modification of ethylene-carbon monoxide interpolymers in analogous fashion to the pyrroles (Section 1.11.4.1.1). The interpolymer was simply treated with acid in a solvent, and magnesium sulfate was added to react with the water formed in the cyclization. As with the pyrroles, the furan units were introduced to improve thermal processing. 

Nickel carbonyl is the more widely known catalyst for the carboxylation reaction dicobalt octacarbonyl has the disadvantage of giving side reactions (15). Dicobalt octacarbonyl has been used in the presence of tributyl phosphine for the reaction of ethylene, carbon monoxide, water, and ethanol. Besides ethyl acetate, acetaldehyde and diethyl ketone were found (136). Hydrogen has been found to increase the rate of reaction (78), presumably by the formation of cobalt hydrocarbonyl. However, this can lead to the formation of aldehydes, as in the reaction of acetyl bromide when an 89.4% yield of aldehyde was obtained in spite of the presence of water (95). 

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