Oligomerization 1-decene

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 ... 

Another recent patent (22) and related patent application (31) cover incorporation and use of many active metals into Si-TUD-1. Some active materials were incorporated simultaneously (e.g., NiW, NiMo, and Ga/Zn/Sn). The various catalysts have been used for many organic reactions [TUD-1 variants are shown in brackets] Alkylation of naphthalene with 1-hexadecene [Al-Si] Friedel-Crafts benzylation of benzene [Fe-Si, Ga-Si, Sn-Si and Ti-Si, see apphcation 2 above] oligomerization of 1-decene [Al-Si] selective oxidation of ethylbenzene to acetophenone [Cr-Si, Mo-Si] and selective oxidation of cyclohexanol to cyclohexanone [Mo-Si], A dehydrogenation process (32) has been described using an immobilized pincer catalyst on a TUD-1 substrate. Previously these catalysts were homogeneous, which often caused problems in separation and recycle. Several other reactions were described, including acylation, hydrogenation, and ammoxidation. 

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. 

Specific catalytic activity of the composites obtained was at least several times higher than the same value for the random copolymer Nafion (even in an esterification reaction considered to be a diffusion-uncontrolled reaction). For the oligomerization reaction of decene-1 with strong diffusion control, the specific catalytic activity of the composites was 35 times higher than that for the random copolymer. Esterification of acrylic acid and alkylation of mesitilene by a substituted phenol were also performed using the composite catalyst. 

Oligomerization of 1-decene in the presence of a silica-BF3-H20 catalyst was shown to yield a mixture of di-, tri- and tetramers that gives a lubricant after hydro-genation. 

The coupling of the unsubstituted carbon atom of the mono-olefin with the Cs chain, which was observed in the co-oligomerization of styrene with butadiene, and of acrylic esters with butadiene, is not, however, a general phenomenon. For example, the co-oligomerization of 1-decene with butadiene using nickel-tricyclohexylphosphine as catalyst leads (after... 

Oligomerization 1-Octene, 1-decene, /8-pinene — TiOz, Zr02, Sn02 145, 176... 

Decomposition of alkylbenzene Ph-Me, Ph-Et, Ph- Pr Friedel-Crafts acylation acetylation, benzoylation, and so on Isomerization of paraffin open-chain C1-C7, cyclic Cs-Cn Esterification -> AcOH + MeOH, EtOH, and so on CgOH + phthalic acid, and so on Cationic polymerization Me, Et, Bu vinyl ether Oligomerization 3-pinene, 1-octene, 1-decene Others -> aldol condensation, and so on... 

Hydrocarboxylation of the Ce-Cs a-olefins with cobaltcarbonyl/pyridine catalysts at 200 °C and 20 MPa gives predominantly the linear carboxylic acids. The acids and their esters are used as additives for lubricants. The Ce-Cio a-olefins are hydroformylated to odd-numbered linear primary alcohols, which are converted to polyvinylchloride (PVC) plasticizers with phthalic anhydride. Oligomerization of (preferably) 1 -decene, applying BF3 catalysts, gives oligomers used as synthetic lubricants known as poly-a-olefins (PAO) or synthetic hydrocarbons (SHC) [11, 12]. The C10-C12 a-olefins can be epoxidized by peracids this opens up a route to bifunctional derivatives or ethoxylates as nonionic surfactants [13]. 

Propene and higher a-olefins also may be dimerized or oligomerized by these catalysts. Generally, reactivity is much lower than that of ethylene and decreases in the order ethylene propylene > 1-butene > 1-hexene > 1-octene > 1-decene. Also the selectivity is lower and mainly branched dimers or oligomers are formed. ... 

Description Polymer-grade ethylene is oligomerized in a liquid-phase reactor (1) with a liquid homogeneous catalyst designed for high activity and selectivity. Liquid effluent and spent catalyst are then separated (2) the liquid is distilled (3) for recycling unreacted ethylene to the reactor, then fractionated (4) in order to produce high-purity alpha olefins. Spent catalyst is treated to remove volatile hydrocarbons before safe disposal. The table below illustrates the superior purities attainable (wt%) with the Alpha-Select process n-Butene-1 >99 n-Hexene-1 >98 n-Octene-1 >96 n-Decene-1 >92... 

Linear (head-to-head) dimerization of a-olefins such as 1-butene, 1-hexene, 1-decene and Chevron Phillips C20-24 a-olefrn mixture can be promoted when less sterically hindered examples of 1 (e.g., Ic) are employed in combination with MAO (Scheme 5.7) [48]. The mechanism for dimerization is thought to involve an initial 1,2-insertion into an iron-hydride bond followed by a 2,1-insertion of the second alkene, and then chain transfer to give the dimers. Structurally related cobalt systems have also been shown to promote dimerization, albeit with lower activities [62]. Oligomerization of the a-olefrns propene, 1-butene and 1-hexene has additionally been achieved with the CF3-containing iron and cobalt systems Ih and 2h yielding highly linear dimers [39]. 

NAFION has been used as an oligomerization catalyst for decene-1 (44). A typical procedure consisted of heating the catalyst (35 g) and decene-1 (140 g) at 120°C for 0.5 hours. After filtering off the catalyst, and partial decene-1 removal, the reaction mixture (114 g) consisted of C-10 (6.8%), C-20 (70.6%), C-30 (19.1%), and C-40 (3.4%). The amount of oligomers was 75.9%. Other olefins that can be oligomerized similarly are 7-tetradecene, octene-2 and decene-5. 

There are no considerable differences between the values of the activation energy (E) and reaction order ( ) of the ozonide thermal decomposition with E-IR and Z-IR (Table 10.7). The smaller E values of the polyiso-prene ozonides in comparison with those of E-BR ozonides and 1-decene ozonide are, most probably, due to the lower thermal stability of small amounts of oligomeric peroxides, which are present among the reaction products of E-IR and Z-IR ozonolysis [36]. 

The system TiCl4-R AlCl3 (n = 1-3, R = alkyl) oligomerizes 1-hexene [940]. Modification with halogenohydrocarbons, phosphoro- and sulfuroorganic compounds, alkali metal hydrides, and nickel salts gave relative catalysts in the 1-decene [783], CH2=CH-(CH2) -CH3 (n = 1-5) [941], Cg-Cna-olefins [942], and Cj-Cg a-olefin oligomerizations [943]. 

The mixed catalytic system TiCl4-Ti(OBu)4-Zr(OBu)4—EtsAljCU (1 2 1 10) oligomerizes with high-yield 1-decene to a product having an average molecular weight of M = 356 [784,838]. 

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