In olefins

The growth of polyolefin fibers continues. Advances in olefin polymerization provide a wide range of polymer properties to the fiber producer. Inroads into new markets are being made through improvements in stabilization, and new and improved methods of extmsion and production, including multicomponent extmsion and spunbonded and meltblown nonwovens. 

Texturing. The final step in olefin fiber production is texturing the method depends primarily on the appHcation. For carpet and upholstery, the fiber is usually bulked, a procedure in which fiber is deformed by hot air or steam jet turbulence in a no22le and deposited on a moving screen to cool. The fiber takes on a three-dimensional crimp that aids in developing bulk and coverage in the final fabric. Stuffer box crimping, a process in which heated tow is overfed into a restricted oudet box, imparts a two-dimensional sawtooth crimp commonly found in olefin staple used in carded nonwovens and upholstery yams. 

Titanium alkoxides are used for the hardening and cross-linking of epoxy, siUcon, urea, melamine, and terephthalate resins in the manufacture of noncorrodable, high temperature lacquers in the sol-gel process as water repellents and adhesive agents (especially with foils) to improve glass surfaces as catalyst in olefin polymeri2ation, and for condensation and esterification. 

Vanadium Alkoxides. Except for the soHd methoxide, the lower vanadium alkoxides are slightly colored, yeUow, or yeUow-brown Hquids. They are easily hydroly2ed and decompose on heating above 100°C they darken. They are made from V20 or VOQ. -Vanadium alkoxides are used mostly in olefin polymeri2ation as catalysts also as hardeners and for coatings. 

A selective poison is one that binds to the catalyst surface in such a way that it blocks the catalytic sites for one kind of reaction but not those for another. Selective poisons are used to control the selectivity of a catalyst. For example, nickel catalysts supported on alumina are used for selective removal of acetjiene impurities in olefin streams (58). The catalyst is treated with a continuous feed stream containing sulfur to poison it to an exacdy controlled degree that does not affect the activity for conversion of acetylene to ethylene but does poison the activity for ethylene hydrogenation to ethane. Thus the acetylene is removed and the valuable olefin is not converted. 

Polymerization. Supported catalysts are used extensively in olefin polymerization, primarily to manufacture polyethylene and polypropylene. Because propylene can polymerize in a stereoregular manner to produce an isotactic, or crystalline, polymer as well as an atactic, or amorphous, polymer and ethylene caimot, there are large differences in the catalysts used to manufacture polyethylene and polypropylene (see Olefin polymers). 

Catalytic Pyrolysis. This should not be confused with fluid catalytic cracking, which is used in petroleum refining (see Catalysts, regeneration). Catalytic pyrolysis is aimed at producing primarily ethylene. There are many patents and research articles covering the last 20 years (84—89). Catalytic research until 1988 has been summarized (86). Almost all catalysts produce higher amounts of CO and CO2 than normally obtained with conventional pyrolysis. This indicates that the water gas reaction is also very active with these catalysts, and usually this leads to some deterioration of the olefin yield. Significant amounts of coke have been found in these catalysts, and thus there is a further reduction in olefin yield with on-stream time. Most of these catalysts are based on low surface area alumina catalysts (86). A notable exception is the catalyst developed in the former USSR (89). This catalyst primarily contains vanadium as the active material on pumice (89), and is claimed to produce low levels of carbon oxides. 

Volume 56 Olefin Polymerization Catalysts. Proceedings of the International Symposium on Recent Developments in Olefin Polymerization Catalysts, Tokyo,... 

The following information was used in olefin plant case studies to determine if the ethylene/propylene cascaded refrigeration systems had enough horsepower for various plant operations. The propylene was condensed against cooling water at 110°F and the ethylene was condensed against propylene at -20°F. For comparison, the horsepower requirements for each refrigerant alone are also shown. 

Reaetions whieh involve the use of hydrogen as a reaetant are termed reduetions, e.g. the addition of a moleeule of hydrogen aeross the unsaturated C=C in olefins to produee saturated alkanes. The material whieh adds hydrogen, or removes oxygen, is termed the redueing agent. 

The dependence of release force on the flexibility of the release layers is noted in systems other than silicones. Recent work in olefin release shows that release is a strong function of the density or crystallinity of the layer [44], At a density above 0.9 g/cm release for an acrylate PSA is greater than 270 g/cm. However, when the density of PE is dropped to 0.865 g/cm-, the release force of the same adhesive construction drops to 35 g/cm. An investigation of interfacial friction and slip in these systems has not yet been reported, but again the manipulation of release rheology greatly impacts the measured peel force. 

Absorption Process for Rejection of Reactor Byproducts Recovery of Monomers from Waste Gas Streams in Olefin Polymerization Process, U.S. Patent 5.681.908. Oct. 28. 1997. 

In certain cases this reduction (with lithium aluminum hydride) takes a different course, and olefins are formed. The effect is dependent on both the reagent concentration and the steric environment of the hydrazone. Dilute reagent and hindered hydrazone favor olefins borohydride gives the saturated hydrocarbon. The hydrogen picked up in olefin formation comes from solvent, and in full reduction one comes from hydride and the other from solvent. This was shown by deuteriation experiments with the hydrazone (150) ... 

Halofluoroalkenes may be prepared by using fluorodihalomethanes or fluoro-halomethanes in olefination procedures similar to those descnbed above. Ruoro-trichloromethane treated with tris(dimethylamino)phosphine forms the corresponding phosphomum salt, which can then be used in the Wirtig procedure. The reaction depends on the nature of the solvent in tetrahydrofuran, little olefination if any occurs however, when benzomtrile is added to the mixture, ylide formation is promoted [50] (equation 48) (Table 19). 

Both diethylphosphonofluoroacetic acid [75] and diethylphosphonofluoroace-tonitnle [76] have been used in olefination procedures (Table 25)... 

Fluoroalkylphosphonates may also be deprotonated for use in olefination reactions with aldehydes [77] (equation 64)... 

Table 11. a-and (3-Fluorinated a, 3-Unsaturated Aldehydes in Olefination Reactions [43 ... 

The most widely accepted mechanism of reaction is shown in the catalytic cycle (Scheme 1.4.3). The overall reaction can be broken down into three elementary steps the oxidation step (Step A), the first C-O bond forming step (Step B), and the second C-O bond forming step (Step C). Step A is the rate-determining step kinetic studies show that the reaction is first order in both catalyst and oxidant, and zero order in olefin. The rate of reaction is directly affected by choice of oxidant, catalyst loadings, and the presence of additives such as A -oxides. Under certain conditions, A -oxides have been shown to increase the rate of reaction by acting as phase transfer catalysts. ... 

In the homogeneous Dimersol process, the olefin conversion is highly dependent on the initial concentration of monomers in the feedstock, which limits the applicability of the process. The biphasic system is able to overcome this limitation and promotes the dimerization of feedstock poorly concentrated in olefinic monomer. 

The overhead stream from the debutanizer or stabilizer is a mix of C, s and C4 s, usually referred to as LPG (liquefied petroleum gas). It is rich in olefins, propylene, and butylene. These light olefins play an important role in the manufacture of reformulated gasoline (RFG). Depending on the refinery s configuration, the cat cracker s LPG is used in the following areas ... 

The phenomenon that early transition metals in combination with alkyl hydroperoxides could participate in olefin epoxidation was discovered in the early 1970s [30, 31]. While m-CPBA was known to oxidize more reactive isolated olefins, it was discovered that allylic alcohols were oxidized to the corresponding epoxides at the same rate or even faster than a simple double bond when Vv or MoVI catalysts were employed in the reaction [Eq. (2)] [30]. 

In essence the active centers for catalytic polymerization of olefins are organometallic complexes of transition metals. For this reason a search for individual organometallic compounds that would possess catalytic activity in olefin polymerization is of great interest. The first attempts to use organometallic compounds of transition metals as catalysts for olefin polymerization were made long ago [e.g. CH3TiCl3 as a catalyst for polymerization of ethylene 116). However, only in recent years as a result of the application of relatively stable organometallic compounds of transition... 

The application of these catalysts in the initial state (without any special treatment of the surface organometallic complexes of such cata-lysts) for ethylene polymerization has been described above. The catalysts formed by the reaction of 7r-allyl compounds with Si02 and AUOj were found to be active in the polymerization of butadiene as well (8, 142). The stereospecificity of the supported catalyst differed from that of the initial ir-allyl compounds. n-Allyl complexes of Mo and W supported on silica were found to be active in olefin disproportionation (142a). 

However, in olefin polymerization by two-component catalysts during polymerization not only active transition metal-polymer bonds are formed, but also inactive aluminum-polymer ones, as a result of the transfer process with the participation of a co-catalyst (11, 162-164). The aluminum-polymer bonds are quenched by tritiated alcohol according to the scheme (25), so an additional tagging of the polymer occurs. The use of iodine (165, 166) as a quenching agent also results in decomposing inactive metal-polymer bonds. 

Two possible reasons may be noted by which just the coordinatively insufficient ions of the low oxidation state are necessary to provide the catalytic activity in olefin polymerization. First, the formation of the transition metal-carbon bond in the case of one-component catalysts seems to be realized through the oxidative addition of olefin to the transition metal ion that should possess the ability for a concurrent increase of degree of oxidation and coordination number (177). Second, a strong enough interaction of the monomer with the propagation center resulting in monomer activation is possible by 7r-back-donation of electrons into the antibonding orbitals of olefin that may take place only with the participation of low-valency ions of the transition metal in the formation of intermediate 71-complexes. 

Unfortunately, at present the information characterizing the properties of the active bond in polymerization catalysts is very scant. The analogy between the features of the active bonds in the propagation centers and those of the transition metal-carbon bond in individual organometallic compounds is sure to exist, but as in the initial form the latter do not show catalytic activity in olefin polymerization this analogy is restricted to its limits. 

The possibility of being involved in olefin metathesis is one of the most important properties of Fischer carbene complexes. [2+2] Cycloaddition between the electron-rich alkene 11 and the carbene complex 12 leads to the intermediate metallacyclobutane 13, which undergoes [2+2] cycloreversion to give a new carbene complex 15 and a new alkene 14 [19]. The (methoxy)phenylcar-benetungsten complex is less reactive in this mode than the corresponding chromium and molybdenum analogs (Scheme 3). 

Although olefin metathesis had soon after its discovery attracted considerable interest in industrial chemistry, polymer chemistry and, due to the fact that transition metal carbene species are involved, organometallic chemistry, the reaction was hardly used in organic synthesis for many years. This situation changed when the first structurally defined and stable carbene complexes with high activity in olefin metathesis reactions were described in the late 1980s and early 1990s. A selection of precatalysts discovered in this period and representative applications are summarized in Table 1. 

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