Propylene-co-carbon monoxide

Poly(propylene-co-carbon monoxide) was prepared by Queisser [2] using [Pd (l,3-bis(diphenylphosphino)propane)(NCCH3)2](BF4)2- Fagon [3] used 1,2-bis(2,3,4,5-tetramethylphospholyl)ethane for preparing poly(ethylene-co-carbon monoxide. 

Poly(carbon monoxide-co- polyolefin), a linear, alternating terpolymer ethylene-co- propylene-co-carbon monoxide Carboxylic rubber... 

Petroleum-based production of -butanol is through the oxo process, which involves first the production of -butyraldehyde by the carboxylation of propylene with carbon monoxide and hydrogen over a rhodium hydrocarbonyl catalyst. Further reduction of -butyraldehyde with hydrogen produces -butanol [4, 6, 7]. Isobutanol is co-produced with -butanol in the oxo process or through the... 

Nitric acid oxidation is used where carbohydrates, ethylene glycol, and propylene are the starting materials. The diaLkyl oxalate process is the newest, where diaLkyl oxalate is synthesized from carbon monoxide and alcohol, then hydrolyzed to oxahc acid. This process has been developed by UBE Industries in Japan as a CO coupling technology in the course of exploring C-1 chemistry. 

Gas-phase oxidation of propylene using oxygen in the presence of a molten nitrate salt such as sodium nitrate, potassium nitrate, or lithium nitrate and a co-catalyst such as sodium hydroxide results in propylene oxide selectivities greater than 50%. The principal by-products are acetaldehyde, carbon monoxide, carbon dioxide, and acrolein (206—207). This same catalyst system oxidizes propane to propylene oxide and a host of other by-products (208). 

Palladium(II) complexes possessing bidentate ligands are known to efficiently catalyze the copolymerization of olefins with carbon monoxide to form polyketones.594-596 Sulfur dioxide is an attractive monomer for catalytic copolymerizations with olefins since S02, like CO, is known to undergo facile insertion reactions into a variety of transition metal-alkyl bonds. Indeed, Drent has patented alternating copolymerization of ethylene with S02 using various palladium(II) complexes.597 In 1998, Sen and coworkers also reported that [(dppp)PdMe(NCMe)]BF4 was an effective catalyst for the copolymerization of S02 with ethylene, propylene, and cyclopentene.598 There is a report of the insertion reactions of S02 into PdII-methyl bonds and the attempted spectroscopic detection of the copolymerization of ethylene and S02.599... 

Ito et al.40 examined the electrochemical reduction of C02 in dimethylsulfoxide (DMSO) with tetraalkylammonium salts at Pb, In, Zn, and Sn under high C02 pressures. At a Pb electrode, the main product was oxalic acid with additional products such as tartaric, malonic, glycolic, propionic, and n-butyric acids, while at In, Zn, and Sn electrodes, the yields of these products were very low (Table 3), and carbon monoxide was verified to be the main product even at a Pt electrode, CO was mainly produced in nonaqueous solvents such as acetonitrile and DMF.41 Also, the products in propylene carbonate42 were oxalic acid at Pb, CO at Sn and In, and substantial amounts of oxalic acid, glyoxylic acid, and CO at Zn, indicating again that the reduction products of C02 depend on the electrode materials used. 

Most recently, Chen et al. studied the solubility of trans-Co2(CO)e[ p-CF3C6H4)3]2 in SCCO2 (p = 0.45 gcm ) in the presence of 0.74 MPa carbon monoxide in view of utilizing this complex as a pre-catalyst for hy-droformylation of ethylene and propylene [123]. The presence of additional P(p-CF3C6H4)3 enabled measurements above 373 K without phosphine dissociation against carbon monoxide. Solubilities were measured between 0.2 mmol cm (353 K) and 2.1 mmol cm (403 K). 

From a retrosynthetic point of view, propylene oxide (PO) and carbon monoxide (CO) are promising building blocks for the production of low-cost PHB (Fig. 13). 

In 1963, Heck reported the ring opening of propylene oxide by the carbonylating reagent tetracarbonylhydridocobalt(I) in the presence of carbon monoxide, which results in a stable acyl cobalttetracarbonyl compound (Fig. 15). However, no polymeric products were reported, which would result from multiple ring opening and CO insertion processes [58, 59]. 

Contrary to the ionic mechanism suggested by Tsuji, an insertion mechanism explains the facts much better. An external attack of carbon monoxide at the most positive carbon atom of propylene in a palladium chloride complex, as Tsuji proposed, would be expected to produce 3-chloro-2-methylpropionyl chloride rather than the observed product, 3-chlorobutyryl chloride. Since oxidation of propylene by Pd (II) ion gives acetone rather than propionalydehyde, a CO insertion reaction and elimination should produce the observed compound, 3-chlorobutyryl chloride... 

The catalyst [Pd(Me-DUPHOS)(MeCN)2](BF4)2 was also effective in the alternating asymmetric copolymerization of aliphatic a-olefins with carbon monoxide [27,28]. The polymer synthesized in a CH3N02-CH30H mixture has both 1,4-ketone and spiroketal (10) units in the main chain. The propylene-CO copolymer consisting only of a 1,4-ketone structure shows [ ]D +22° (in (CF3)2CHOH), and the optical purity of the main chain chiral centers is over 90% as estimated by NMR analysis using a chiral Eu shift reagent. 

The corresponding acyl derivatives, [Rh6(CO)i5(COR)]- (R = Et, Pr), were originally obtained as stable solutions of the hydronium salts by reaction of Rhi(CO)i2 with water in the presence of a mixture of carbon monoxide and an olefin such as ethylene or propylene (43) ... 

Preferred olefins in the polymerisation are one or more of ethylene, propylene, 1-butene, 2-butene, 1-hexene, 1-octene, 1-pentene, 1-tetradecene, norbornene and cyclopentene, with ethylene, propylene and cyclopentene. Other monomers that may be used with these catalysts (when it is a Pd(II) complex) to form copolymers with olefins and selected cycloolefins are carbon monoxide (CO) and vinyl ketones of the general formula H2C=CHC(0)R. Carbon monoxide forms alternating copolymers with the various olefins and cycloolefins. 

More universal is the method of Cp determination using selective tracers such as carbon monoxide and carbon dioxide which interact only with active metal = polymer bondsUsing tagged CO and CO2 as quenching agents systematic data have been accumulated so far on the influence of the composition of catalysts (titanium chlorides with various organometallic compounds) and polymerization conditions on Cp and kp values for the polymerization of ethylene and propylene IS)... 

The same types of compounds were generated in the pyrolysis of poly(propylene-a/f-carbon monoxide). The pyrolysis products also consist of several small molecules (HjO, CO, CsHe), ketones, and cyclic compounds. Their proportions are given in Table 6.8 3 [4J. 

Desulfurization of petroleum feedstock (FBR), catalytic cracking (MBR or FI BR), hydrodewaxing (FBR), steam reforming of methane or naphtha (FBR), water-gas shift (CO conversion) reaction (FBR-A), ammonia synthesis (FBR-A), methanol from synthesis gas (FBR), oxidation of sulfur dioxide (FBR-A), isomerization of xylenes (FBR-A), catalytic reforming of naphtha (FBR-A), reduction of nitrobenzene to aniline (FBR), butadiene from n-butanes (FBR-A), ethylbenzene by alkylation of benzene (FBR), dehydrogenation of ethylbenzene to styrene (FBR), methyl ethyl ketone from sec-butyl alcohol (by dehydrogenation) (FBR), formaldehyde from methanol (FBR), disproportionation of toluene (FBR-A), dehydration of ethanol (FBR-A), dimethylaniline from aniline and methanol (FBR), vinyl chloride from acetone (FBR), vinyl acetate from acetylene and acetic acid (FBR), phosgene from carbon monoxide (FBR), dichloroethane by oxichlorination of ethylene (FBR), oxidation of ethylene to ethylene oxide (FBR), oxidation of benzene to maleic anhydride (FBR), oxidation of toluene to benzaldehyde (FBR), phthalic anhydride from o-xylene (FBR), furane from butadiene (FBR), acrylonitrile by ammoxidation of propylene (FI BR)... 

Maximum yield of propylene, which occurs near the higher temperature, according to Calderbank et al (9), is only 8.5 wt %, and this is accompanied by 5 wt % ethylene as a co-product. Above 950°F, oxidative cracking is the main reaction, and while yields of light paraffins and unsaturates result, almost no propylene and large amounts of carbon monoxide become the product distribution. 

Cobalt compounds are useful chemical catalysts for the synthesis of fuels (Fi-scher-Tropsch process), the synthesis of alcohols and aldehydes from olefins, hydrogen and carbon monoxide at elevated temperatures and pressures ( oxo process , hydroformylation ). They are also used in petroleum refining and the oxidation of organic compounds. In the oxo process, cobalt carbonyl, Co2(CO)g, is employed or generated in situ. For the selective production of n-butanol from propylene, hydrogen and CO, an organophosphine-modified cobalt carbonyl complex is used as the catalyst. Cobalt salts are proven oxidation catalysts examples include the production of terephthalic acid by the oxidation of p-xylene, and the manufacture of phenol by the oxidation of toluene. 

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