Mixed Octenes

PROPERTIES TECHNICAL GRADE PROPERTIES PURE GRADE TECHNICAL GRADE 

Composition, weight percent Composition, weight percent  

Purity by freezing point, mol % 95.0 95.0 min Purity by freezing point, mol %  

Initial boiling ooint 257 Initial boiling point 257.0 256.9 

Vapor pressure at 70 F, psia Vapor pressure et 70 F.psia  

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Dimersol X A process for dimerizing mixed butenes to mixed octenes. Selective hydrogenation, catalyzed by a soluble Ziegler catalyst, is used. The spent catalyst is discarded. The process was developed by IFP and first operated at Kashima, Japan, in 1980. BASF has used the process in Ludwigshafen since 1985. 

Propjiene (qv) [115-07-1] is the predominant 0x0 process olefin feedstock. Ethylene (qv) [74-85-1J, as well as a wide variety of terminal, internal, and mixed olefin streams, are also hydroformylated commercially. Branched-chain olefins include octenes, nonenes, and dodecenes from fractionation of oligomers of C —C olefins as well as octenes from dimerization and codimerization of isobutylene and 1- and 2-butenes (see Butylenes). 

Chlorooctane (14 9 g, 0 I mol), potassium fluoride dihydrate (47 g, 0 5 mol), hexadecyltributylphosphonium bromide (5 1 g, 0 01 mol), and water (30 mL) are mixed in an autoclave equipped with a magnetic stirrer and heated to 160 °C (bath temperature) for 7 h After this time gas-liquid chromatographic analysis (10% Carbowax 20M on Chromosorb) shows a 95% conversion to a mixture of 1-fluorooctane (82%), octenes (6%), and 1-octanol (7%) The organic layer is separated, washed with water, washed with concentrated sulfuric acid, washed once again with water, dried over calcium chloride, and distilled to give 10 g (77%) of ] -fluorooctane... 

The reaction takes place at low temperature (40-60 °C), without any solvent, in two (or more, up to four) well-mixed reactors in series. The pressure is sufficient to maintain the reactants in the liquid phase (no gas phase). Mixing and heat removal are ensured by an external circulation loop. The two components of the catalytic system are injected separately into this reaction loop with precise flow control. The residence time could be between 5 and 10 hours. At the output of the reaction section, the effluent containing the catalyst is chemically neutralized and the catalyst residue is separated from the products by aqueous washing. The catalyst components are not recycled. Unconverted olefin and inert hydrocarbons are separated from the octenes by distillation columns. The catalytic system is sensitive to impurities that can coordinate strongly to the nickel metal center or can react with the alkylaluminium derivative (polyunsaturated hydrocarbons and polar compounds such as water). 

Structurally, plastomers straddle the property range between elastomers and plastics. Plastomers inherently contain some level of crystallinity due to the predominant monomer in a crystalline sequence within the polymer chains. The most common type of this residual crystallinity is ethylene (for ethylene-predominant plastomers or E-plastomers) or isotactic propylene in meso (or m) sequences (for propylene-predominant plastomers or P-plastomers). Uninterrupted sequences of these monomers crystallize into periodic strucmres, which form crystalline lamellae. Plastomers contain in addition at least one monomer, which interrupts this sequencing of crystalline mers. This may be a monomer too large to fit into the crystal lattice. An example is the incorporation of 1-octene into a polyethylene chain. The residual hexyl side chain provides a site for the dislocation of the periodic structure required for crystals to be formed. Another example would be the incorporation of a stereo error in the insertion of propylene. Thus, a propylene insertion with an r dyad leads similarly to a dislocation in the periodic structure required for the formation of an iPP crystal. In uniformly back-mixed polymerization processes, with a single discrete polymerization catalyst, the incorporation of these intermptions is statistical and controlled by the kinetics of the polymerization process. These statistics are known as reactivity ratios. 

Octol A process for making mixed linear octenes by the catalytic dimerization of mixed butenes. A proprietaiy heterogeneous catalyst is used. Developed jointly by Hiils and UOP, and now offered for license by UOP. First operated in 1983 in the Hiils refinery in Marl, Germany. Another installation began production in 1986 at the General Sekiyu Refineries in Japan. 

An equimolal mixture of octenes and hydrogen is fed to a fluidized bed of catalyst at 2 atm. Find the required weight of catalyst per unit of feed, Wc/F0, as a function of conversion in (a) plug flow (b) a completely mixed bed. 

Fig. 10 Effect of trans-4-octene and -nonanal on the mixing behaviour of TMS addition of 15wt% transA-octene at reaction temperature (125 °C) and 17wt% nonanal at separating temperature (25 °C)...

In the first set of experiments O. Nuyken et al. studied the rhodium-catalyzed hydroformylation of 1-octene to its corresponding -aldehyde (Scheme 6.5) [51-53]. The active catalyst species was formed in situ by mixing the appropriate amount of polymeric macroligand, Rh(CO)2acac and 1-octene in water. The results are summarized in Tab. 6.3. 

Substantial alkenyl hydroperoxide concentrations build up in 1-hexa-decene, 2-octene, mixed internal olefins, and mixed Ci4-Ci6 alpha-olefins... 

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