By oligomerization

One of the mam uses of the linear a olefins prepared by oligomerization of ethylene is in the preparation of linear low density polyethylene Linear low density polyethylene is a copoly mer produced when ethylene is polymerized in the presence of a linear a olefin such as 1 decene [H2C=CH(CH2)7CH3] 1 Decene replaces ethylene at random points in the growing polymer chain Can you deduce how the structure of linear low density polyethylene differs from a linear chain of CH2 units ... 

Manufacture of Monomers. The monomers of the greatest interest are those produced by oligomerization of ethylene (qv) and propylene (qv). Some olefins are also available as by-products from refining of petroleum products or as the products of hydrocarbon (qv) thermal cracking. 

Addition. Addition reactions of ethylene have considerable importance and lead to the production of ethylene dichloride, ethylene dibromide, and ethyl chloride by halogenation—hydrohalogenation ethylbenzene, ethyltoluene, and aluminum alkyls by alkylation a-olefms by oligomerization ethanol by hydration and propionaldehyde by hydroformylation. 

Homologous even-numbered n-a-olefins by oligomerization processes of ethylene... 

Coordination-catalyzed ethylene oligomerization into n-a-olefins. The synthesis of homologous, even-numbered, linear a-olefins can also be performed by oligomerization of ethylene with the aid of homogeneous transition metal complex catalysts [26]. Such a soluble complex catalyst is formed by reaction of, say, a zero-valent nickel compound with a tertiary phosphine ligand. A typical Ni catalyst for the ethylene oligomerization is manufactured from cyclo-octadienyl nickel(O) and diphenylphosphinoacetic ester ... 

Baler, R., Dahl, G., Voellmy, R. (1993). Activation of human heat shock genes is accompanied by oligomerization, modification, and rapid translocation of heat shock transcription factor HSFI. Mol. Cell. Biol. 13.2486-2496. 

The third class of hydraulic fluids discussed in this profile is the polyalphaolefins. Polyalphaolefins are synthetic hydrocarbons that are made by oligomerizing alphaolefins such as 1-decene (see Chapters 3,4, and 5). Aliphatic hydrocarbons are the principal components of both mineral oils and polyalphaolefins, but the array of hydrocarbons with differing molecular weights is much narrower in polyalphaolefins than in mineral oils. Certain polyalphaolefins maintain good operational characteristics at low temperatures and have been proposed for use in hydraulic systems in U.S. military aircraft (Kinkead et al. 1992b). 

Polyalphaolefin Hydraulic Fluids. Polyalphaolefms are made by oligomerizing alphaolefins such as 1-decene in the presence of a catalyst (Newton 1989 Shubkin 1993 Wills 1980). The crude reaction mixture is quenched with water, hydrogenated, and distilled. The number of monomer units present in the product polyalphaolefin oil depends on a number of reaction parameters including the type of catalyst, reaction temperature, reaction time, and pressure (Shubkin 1993). The exact combination of reaction parameters used by a manufacturer is tailored to fit the end-use of the resulting polyalphaolefin oil. A typical polyalphaolefin oil prepared from 1-decene and BF3- -C4H9OH catalyst at 30 °C contains predominantly trimer (C30 hydrocarbons) with much smaller amounts of dimer, tetramer, pentamer, and hexamer. While 1-decene is the most common starting material, other alphaolefins can be used, depending on the needs of the product oil. 

Oligomerization of nucleobases can be advantageous to reinforce the H-bonding supramolecular motifs when supramacromolecular polymers are desired. Moreover the different interconverting outputs that may form by oligomerization define a dynamic polyfunctional diversity which may be extracted selectively under the intrinsic stability of the system or by interaction with external factors by polymerization in the solid state. 

De Klerk, A. 2006. Distillate production by oligomerization of Fischer-Tropsch olefins over solid phosphoric acid. Energy Fuels 20 439 -5. 

However, an important problem arises during the peroxidative removal of phenols from aqueous solutions PX is inactivated by free radicals, as well as by oligomeric and polymeric products formed in the reaction, which attach themselves to the enzyme (Nazari and others 2007). This suicide peroxide inactivation has been shown to reduce the sensitivity and efficiency of PX. Several techniques have been introduced to reduce the extent of suicide inactivation and to improve the lifetime of the active enzyme, such as immobilization. Moreover, Nazari and others (2007) reported a mechanism to prevent and control the suicide peroxide inactivation of horseradish PX by means of the activation and stabilization effects of Ni2+ ion, which was found to be useful in processes such as phenol removal and peroxidative conversion of reducing substrates, in which a high concentration of hydrogen peroxide may lead to irreversible enzyme inactivation. 

SHOP [Shell Higher Olefins Process] A process for producing a-olefins by oligomerizing ethylene, using a proprietary rhodium/phosphine catalyst. The a-olefins can then be iso-merized to internal olefins as required. Invented by W. Keim in the Institut fur Technische Chemie und Petrolchemie, Aachen, in the 1970s. The first plant was built in Geismar, LA, in 1979 the second in Stanlow, Cheshire, in 1982. Licensed worldwide by a consortium of Union Carbide, Davy-McKee, and Johnson Matthey. 

Paushkin, S. V., Kushnirov, V. V., Smirnov, V. N., and Ter-Avanesyan, M. D. (1996). Propagation of the yeast prion-like psi] determinant is mediated by oligomerization of the SUP35-encoded polypeptide chain release factor. EMBO J. 15, 3127-3134. 

Dehydration into ethylene (over acid catalysts) [71-73] followed by oligomerization (via coordination or multifunctional catalysis) [74-77]. The main problem is the need to remove water from the feed and the vaporization of ethanol, making the process costly. 

Figure 13.15 Photomicrographs of PET filaments showing surface breaks caused by oligomeric contaminants [9]. Photographs provided by W. Goltner...

Figure 4.3 Reaction of wood with maleic anhydride, followed by oligomerization of the activated wood with epoxide and maleic anhydride.

Alpha olefins are made either by oligomerization, growing them on an aluminum root by adding ethylene until the desire size is reached, or by catalytic processes, one favoring the shorter alpha olefins. 

Double bond isomerization using molecular sieves (5A) was reported in the patent literature by Fleck and Wight of Union Oil Company [34] only a few years after synthetic zeolites became commercially available. More recently [35] ferrierite has also been claimed. The major initial uses were to convert a-olefins (1-olefins) into mixtures of internal olefins for further conversion, usually by oligomerization into various products-lube oil base stocks predominating. Inevitably, patents were issued noting the ability to convert internal olefins into mixtures containing greater concentrations of 1-olefins (e.g., [36]), but few practical processes have resulted. 

Table V summarizes rate constants, and activation volumes for water exchange on [M(0H)(H20)5] together with those of [M(H20)6] . Accuracy of exchange rate constants /jqh and its activation parameters AH and AS relies on the knowledge of AHj , and ASa° (39,52). The hydrolysis of aqueous M " " ions is complicated by oligomerization and ranges of hydrolysis constants have been reported for example for Al (91,92) and Ga (93-95). As a general trend a strong increase in the lability of the coordinated water molecules is observed for the hydrolyzed species when compared to the hexa-aqua ions. Even at very low pH, where the mole fraction of the hydrolyzed species is extremely small, the water exchange observed by NMR on the bulk water can be dominated by the fast exchange on [M(0H)(H20)5] and not by the much slower exchange on...

Branched Primary Alcohol Ethoxylates (BPAE). The hydrophobes of BPAE are produced by oligomerization of propylene or butene followed by catalytic addition of CO and H2 to yield highly branched alcohols. The ethoxylates of these alcohols biodegrade more slowly and less extensively than the linear alcohol ethoxylates (11.12). 

Linear hydrocarbons with a double bond at the end of the chain are made by oligomerization of ethylene. Compounds with 6-18 carbons are the most popular. Ziegler catalysts are used in this process. Note that certain olefins... 

The hard-soft block copolymer approach employed to produce segmental PUs (Section 7.6) has also been used with polyesters, with the hard block formed from 1,4-butadienediol and terephthalic acid while the soft block is provided by oligomeric (approximate molecular weight of 2000 Da) poly(tetramethylene glycol) and is sold under the trade name Hytrel. 

Leaching of the ionic liquid from the support was negligible. However, deactivation was observed, caused by moisture present during product separation (which can be minimized with proper care) and by oligomerization of dodecene on the catalyst surface. Unfortunately, both factors cause irreversible loss of catalytic activity. 

MI1). The proposed route involves photoisomerization of DAMN to 9, followed by addition of another mole of HCN to give adenine. Adenine can also be prepared by oligomerization of HCN in liquid ammonia in 24% yield and from DAMN and formamidine acetate in 55% yield (72USP3671649). In a definitive paper, Shuman et al. show that 10, as well as 9, is an intermediate to adenine in the nonphotochemical route (Scheme 3) (79JOC4532). 

Because of their very similar boiling points and azeotrope formation, the components of the C4 fraction cannot be separated by distillation. Instead, other physical and chemical methods must be used. 1,3-Butadiene is recovered by complex formation or by extractive distillation.143-146 Since the reactivity of isobutylene is higher than that of n-butenes, it is separated next by chemical transformations. It is converted with water or methyl alcohol to form, respectively, tert-butyl alcohol and tert-butyl methyl ether, or by oligomerization and polymerization. The remaining n-butenes may be isomerized to yield additional isobutylene. Alternatively, 1-butene in the butadiene-free C4 fraction is isomerized to 2-butenes. The difference between the boiling points of 2-butenes and isobutylene is sufficient to separate them by distillation. n-Butenes and butane may also be separated by extractive distillation.147... 

Oligomerization of Ethylene. 1-Butene is a small by-product in the production of linear alpha-olefins by oligomerization of ethylene. Linear alpha-olefins have one double bond at the terminal position and comprise the homologous series of compounds with carbon atoms between 4 and 19. The primary use of alpha-olefins is in the detergent industry. About 245,000 t/yr of 1-butene was produced for chemical use in the Gulf Coast of the United States in 1988 (72). 

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