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Vinyl acetate catalysts

The following rate expressions were derived from the experimental kinetic, data in Samanos et al. (1971) for a particular vinyl acetate catalyst. [Pg.322]

Recently, rhodium/poly(enolate-co-vinyl alcohol-co-vinyl acetate) catalysts have been developed for the biphasic hydroformylation of aliphatic alkenes and applied to the selective hydroformylation of functionalized alkenes [16], Although the conversions were low (< 25%), excellent selectivities for the hydroformylation of n-bu-tyl vinyl ether and methyl 3,3-dimethylpenten-4-onate can be achieved with such water-soluble polymer-anchored rhodium catalysts. For instance, the hydroformylation of methyl 3,3-dimethylpenten-4-onate gives only the linear aldehyde. [Pg.412]

The feedstock requirements for the oxygen based vinyl acetate process are calculated based on the stoichiometry and catalyst selectivity for the reaction of ethylene and acetic acid with oxygen to vinyl acetate. Catalyst selectivity is about 90% for ethylene to vinyl acetate. A small amount of acetaldehyde and other hydrocarbon byproducts are formed. However, for simplification of the calculation it is assumed that the remainder of the ethylene reacts to form carbon dioxide and water vapor. This gives a slightly higher quantity of oxygen than accounting for all of the by-... [Pg.186]

The main difference from academic catalyst preparation is that in industry only a limited number of unit operations are used and therefore, several highly sophisticated lab preparation techniques, unless they result in extraordinary catalysts, cannot be applied in industry. Moreover, economic factors (costs of precursor materials) and ecological demands (avoid toxic and environmentally harmful waste) have to be considered. In fact, most catalysts in industry are manufactured by impregnation, precipitation, or ion-exchange techniques. Recently, Degussa has published some features of their high-throughput synthesis equipment illustrated by preparation of an advanced Pd-based vinyl acetate catalysts [109,118). [Pg.235]

Vinyl acetate reacts with the alkenyl triflate 65 at the /3-carbon to give the 1-acetoxy-1,3-diene 66[68]. However, the reaction of vinyl acetate with 5-iodo-pyrimidine affords 5-vinylpyrimidine with elimination of the acetoxy group[69]. Also stilbene (67) was obtained by the reaction of an excess of vinyl acetate with iodobenzene when interlamellar montmorillonite ethylsilyl-diphenylphosphine (L) palladium chloride was used as an active catalyst[70]. Commonly used PdCl2(Ph3P)2 does not give stilbene. [Pg.138]

The reactant corresponding to retrosynthetic path b in Scheme 2.2 can be obtained by Meerwein arylation of vinyl acetate with o-nitrophcnyldiazonium ions[9], Retrosynthetic path c involves oxidation of a 2-(o-nitrophenyl)ethanol. This transformation has also been realized for 2-(o-aminophenyl)ethanols. For the latter reaction the best catalyst is Ru(PPhj)2Cl2. The reaction proceeds with evolution of hydrogen and has been shown to be applicable to a variety of ring-substituted 2-(o-aminophenyl)ethanols[10]. [Pg.15]

This oxidation process for olefins has been exploited commercially principally for the production of acetaldehyde, but the reaction can also be apphed to the production of acetone from propylene and methyl ethyl ketone [78-93-3] from butenes (87,88). Careflil control of the potential of the catalyst with the oxygen stream in the regenerator minimises the formation of chloroketones (94). Vinyl acetate can also be produced commercially by a variation of this reaction (96,97). [Pg.52]

Olefins add anhydrous acetic acid to give esters, usually of secondary or tertiary alcohols propjiene [115-07-1] yields isopropyl acetate [108-21-4], isobutjiene [115-11-7] gives tert-huty acetate [540-88-5]. Minute amounts of water inhibit the reaction. Unsaturated esters can be prepared by a combined oxidative esterification over a platinum group metal catalyst. Eor example, ethylene-air-acetic acid passed over a palladium—Hthium acetate catalyst yields vinyl acetate. [Pg.66]

Acetylation of acetaldehyde to ethyUdene diacetate [542-10-9], a precursor of vinyl acetate, has long been known (7), but the condensation of formaldehyde [50-00-0] and acetic acid vapors to furnish acryflc acid [97-10-7] is more recent (30). These reactions consume relatively more energy than other routes for manufacturing vinyl acetate or acryflc acid, and thus are not likely to be further developed. Vapor-phase methanol—methyl acetate oxidation using simultaneous condensation to yield methyl acrylate is still being developed (28). A vanadium—titania phosphate catalyst is employed in that process. [Pg.66]

Liquid- and vapor-phase processes have been described the latter appear to be advantageous. Supported cadmium, zinc, or mercury salts are used as catalysts. In 1963 it was estimated that 85% of U.S. vinyl acetate capacity was based on acetylene, but it has been completely replaced since about 1982 by newer technology using oxidative addition of acetic acid to ethylene (2) (see Vinyl polymers). In western Europe production of vinyl acetate from acetylene stiU remains a significant commercial route. [Pg.102]

Raw Material. PVA is synthesized from acetjiene [74-86-2] or ethylene [74-85-1] by reaction with acetic acid (and oxygen in the case of ethylene), in the presence of a catalyst such as zinc acetate, to form vinyl acetate [108-05-4] which is then polymerized in methanol. The polymer obtained is subjected to methanolysis with sodium hydroxide, whereby PVA precipitates from the methanol solution. [Pg.337]

Hydrocarbon resins (qv) are prepared by copolymerization of vinyltoluene, styrene, and a-methylstyrene in the presence of a Eriedel-Crafts catalyst (AlCl ). These resins are compatible with wax and ethylene—vinyl acetate copolymer (197). [Pg.563]

The metals are impregnated together or separately from soluble species, eg, Na2PdCl4 and HAuCl or acetates (159), and are fixed by drying or precipitation prior to reduction. In some instances sodium or potassium acetate is added as a promoter (160). The reaction of acetic acid, ethylene, and oxygen over these catalysts at ca 180°C and 618—791 kPa (75—100 psig) results in the formation of vinyl acetate with 92—94% selectivity the only other... [Pg.385]

Vinyl ethers are prepared in a solution process at 150—200°C with alkaH metal hydroxide catalysts (32—34), although a vapor-phase process has been reported (35). A wide variety of vinyl ethers are produced commercially. Vinyl acetate has been manufactured from acetic acid and acetylene in a vapor-phase process using zinc acetate catalyst (36,37), but ethylene is the currently preferred raw material. Vinyl derivatives of amines, amides, and mercaptans can be made similarly. A/-Vinyl-2-pyrroHdinone is a commercially important monomer prepared by vinylation of 2-pyrroHdinone using a base catalyst. [Pg.374]

Vinyl acetate (ethenyl acetate) is produced in the vapor-phase reaction at 180—200°C of acetylene and acetic acid over a cadmium, 2inc, or mercury acetate catalyst. However, the palladium-cataly2ed reaction of ethylene and acetic acid has displaced most of the commercial acetylene-based units (see Acetylene-DERIVED chemicals Vinyl polymers). Current production is dependent on the use of low cost by-product acetylene from ethylene plants or from low cost hydrocarbon feeds. [Pg.393]

Catalysts. Mercury is or has been used in the catalysis (qv) of various plastics, including polyurethane [26778-67-6] poly(vinyl chloride) [9002-86-2] and poly(vinyl acetate) [9003-20-7]. Most poly(vinyl chloride) and poly(vinyl acetate) is manufactured by processes that do not use mercury (3). [Pg.110]

Until about 1980, mercuric chloride was used extensively as a catalyst for the preparation of vinyl chloride from acetjiene (7). Since the early 1980s, vinyl chloride and vinyl acetate have been prepared from ethylene instead of acetjiene, and the use of mercuric chloride as a catalyst has practically disappeared. [Pg.113]

The use of TAG as a curing agent continues to grow for polyolefins and olefin copolymer plastics and mbbers. Examples include polyethylene (109), chlorosulfonated polyethylene (110), polypropylene (111), ethylene—vinyl acetate (112), ethylene—propylene copolymer (113), acrylonitrile copolymers (114), and methylstyrene polymers (115). In ethylene—propylene copolymer mbber compositions. TAG has been used for injection molding of fenders (116). Unsaturated elastomers, such as EPDM, cross link with TAG by hydrogen abstraction and addition to double bonds in the presence of peroxyketal catalysts (117) (see Elastol rs, synthetic). [Pg.88]

Manufacture. PVBs are manufactured by a variety of two-stage heterogeneous processes. In one of these an alcohol solution of poly(vinyl acetate) and an acid catalyst are heated to 60—80°C with strong agitation. As the poly(vinyl alcohol) forms, it precipitates from solution (77). Ethyl acetate, the principle by-product, is stripped off and sold. The precipitated poly(vinyl alcohol) is washed to remove by-products and excess acid. The poly(vinyl alcohol) is then suspended in a mixture of ethyl alcohol, butyraldehyde, and mineral acid at temperatures above 70°C. As the reaction approaches completion the reactants go into solution. When the reaction is complete, the catalyst is neutralized and the PVB is precipitated from solution with water, washed, centrifuged, and dried. Resin from this process has very low residual vinyl acetate and very low levels of gel from intermolecular acetalization. [Pg.452]

Hydrolysis of vinyl acetate is catalyzed by acidic and basic catalysts to form acetic acid and vinyl alcohol which rapidly tautomerizes to acetaldehyde. This rate of hydrolysis of vinyl acetate is 1000 times that of its saturated analogue, ethyl acetate, ia alkaline media (15). The rate of hydrolysis is minimal at pH 4.44 (16). Other chemical reactions which vinyl acetate may undergo are addition across the double bond, transesterification to other vinyl esters, and oxidation (15—21). [Pg.459]

The catalysts most often described in the literature (209—211,252) are sodium or potassium hydroxide, methoxide, or ethoxide. The reported ratio of alkali metal hydroxides or metal alcoholates to that of poly(vinyl acetate) needed for conversion ranges from 0.2 to 4.0 wt % (211). Acid catalysts ate normally strong mineral acids such as sulfuric or hydrochloric acid (252—254). Acid-cataly2ed hydrolysis is much slower than that of the alkaline-cataly2ed hydrolysis, a fact that has limited the commercial use of these catalysts. [Pg.484]

In the slurry process, the hydrolysis is accompHshed using two stirred-tank reactors in series (266). Solutions of poly(vinyl acetate) and catalyst are continuously added to the first reactor, where 90% of the conversion occur, and then transferred to the second reactor to reach hiU conversion. Alkyl acetate and alcohols are continuously distilled off in order to drive the equiUbrium of the reaction. The resulting poly(vinyl alcohol) particles tend to be very fine, resulting in a dusty product. The process has been modified to yield a less dusty product through process changes (267,268) and the use of additives (269). Partially hydroly2ed products having a narrow hydrolysis distribution cannot be prepared by this method. [Pg.485]

In the screw conveyor process, solutions of poly(vinyl acetate) and catalyst are mixed in a high intensity mixer and continuously introduced to a screw-type saponification and conveyor system (270). Downstream details are similar to those found in the belt process. [Pg.485]

Alternatively, thermal cracking of acetals or metal-catalyzed transvinylation can be employed. Vinyl acetate or MVE can be employed for transvinylation and several references illustrate the preparation especially of higher vinyl ethers by such laboratory techniques. Special catalysts and conditions are required for the synthesis of the phenol vinyl ethers to avoid resinous condensation products (6,7). Direct reaction of ethylene with alcohols has also been investigated (8). [Pg.514]

The cadmium chalcogenide semiconductors (qv) have found numerous appHcations ranging from rectifiers to photoconductive detectors in smoke alarms. Many Cd compounds, eg, sulfide, tungstate, selenide, teUuride, and oxide, are used as phosphors in luminescent screens and scintiUation counters. Glass colored with cadmium sulfoselenides is used as a color filter in spectroscopy and has recently attracted attention as a third-order, nonlinear optical switching material (see Nonlinear optical materials). DiaLkylcadmium compounds are polymerization catalysts for production of poly(vinyl chloride) (PVC), poly(vinyl acetate) (PVA), and poly(methyl methacrylate) (PMMA). Mixed with TiCl, they catalyze the polymerization of ethylene and propylene. [Pg.392]


See other pages where Vinyl acetate catalysts is mentioned: [Pg.191]    [Pg.58]    [Pg.3]    [Pg.62]    [Pg.829]    [Pg.830]    [Pg.843]    [Pg.851]    [Pg.933]    [Pg.191]    [Pg.58]    [Pg.3]    [Pg.62]    [Pg.829]    [Pg.830]    [Pg.843]    [Pg.851]    [Pg.933]    [Pg.419]    [Pg.20]    [Pg.37]    [Pg.530]    [Pg.68]    [Pg.385]    [Pg.355]    [Pg.479]    [Pg.404]    [Pg.404]    [Pg.202]    [Pg.455]    [Pg.482]    [Pg.396]    [Pg.52]    [Pg.102]   
See also in sourсe #XX -- [ Pg.6 , Pg.306 ]




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