Material vinyl acetate monomer process

The industrial process for the vapor-phase manufacture of vinyl acetate monomer is quite common (Daniels, 1989) and utilizes widely available raw materials. Vinyl acetate is used chiefly as a monomer to make polyvinyl acetate and other copolymers. Hoechst-Celanese, Union Carbide, and Quantum Chemical are reported U.S. manufacturers. DuPont also currently operates a vinyl acetate process at its plant in LaPorte, Texas. To protect any proprietary DuPont information, all of the physical property and kinetic data, process flowsheet information, and modeling formulation in the published paper come from sources... 

A recent interesting example of the use of alkane feedstocks to develop more sustainable processes is the direct conversion of ethane into acetic acid developed by Sabic. Acetic acid is the raw material for many key petrochemical intermediates and products, including vinyl acetate monomer (VAM), purified terephthalic acid (PTA), acetate esters, cellulose acetate, acetic anhydride, monochloroacetic acid (MCA), and so on. Acetic acid is produced commercially from several feedstocks and by several different technologies. 

We will begin with the carbonylation of Mel which in situ is generated from MeOH for acetic acid production because of its industrial importance. Acetic acid is an important chemical commodity with a wide range of appUcations in organic chemistry. In organic synthesis, acetic acid is mainly used as a raw material for vinyl acetate monomers and acetic anhydride synthesis, as well as a solvent for producing terephthalic acid from xylene via the oxidation process. In 1998 the world s capacity of acetic acid production was approximately 7.8 milUon tons, of which more than 50 % were produced by BP-Amoco and Celanese. 

The two-carbon short-chain acetic acid is start material for the production of vinyl acetate monomer (VAM). This application consumes one third of the world s production of acetic acid (Cheung et al. 2005). The product of the condensation of two molecules of acetic acid is acetic anhydride. The worldwide production of acetic anhydride is a further major application and uses approximately 25-30 % of the global production of acetic acid. The main process involves dehydration of acetic acid to give ketene at the temperature of 700-750 °C. Ketene is thereafter reacted with acetic acid to obtain the anhydride (Held et al. 2005). Acetic anhydride is an acetylation agent. As such, its major application is for cellulose acetate, a... 

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. 

The principal chemical markets for acetylene at present are its uses in the preparation of vinyl chloride, vinyl acetate, and 1,4-butanediol. Polymers from these monomers reach the consumer in the form of surface coatings (paints, films, sheets, or textiles), containers, pipe, electrical wire insulation, adhesives, and many other products which total biUions of kg. The acetylene routes to these monomers were once dominant but have been largely displaced by newer processes based on olefinic starting materials. 

In poly(vinyl acetate) copolymer emulsions, the properties are significantly affected by the composition of the aqueous phase and by the stabilizers and buffers used iu the preparation of these materials, along with the process conditions (eg, monomer concentrations, pH, agitation, and temperature). The emulsions are milk-white Hquids containing ca 55 wt % PVAc, the balance being water and small quantities of wetting agents or protective coUoids. 

Polymerization Processes. Vinyl acetate has been polymerized industrially by bulk, solution, suspension, and emulsion processes (34). Perhaps 90% of the material identified as poly(vinyl acetate) or copolymers that are predominantly vinyl acetate are made by emulsion techniques. Detailed information is in patent and scientific Hterature and in procedures available in the brochures from monomer producing companies (15,34). 

Over the past years considerable attention has been paid to the dispersing system since this controls the porosity of the particle. This is important both to ensure quick removal of vinyl chloride monomer after polymerisation and also to achieve easy processing and dry blendable polymers. Amongst materials quoted as protective colloids are vinyl acetate-maleic anhydride copolymers, fatty acid esters of glycerol, ethylene glycol and pentaerythritol, and, more recently, mixed cellulose ethers and partially hydrolysed polyfvinyl acetate). Much recent emphasis has been on mixed systems. 

Because the polymer degrades before melting, polyacrylonitrile is commonly formed into fibers via a wet spinning process. The precursor is actually a copolymer of acrylonitrile and other monomer(s) which are added to control the oxidation rate and lower the glass transition temperature of the material. Common copolymers include vinyl acetate, methyl acrylate, methyl methacrylate, acrylic acid, itaconic acid, and methacrylic acid [1,2]. 

Copolymerization. Vinyl chloride can be copolymerized with a variety of monomers. Vinyl acetate, the most important commercial comonomer, is used to reduce crystallinity, winch aids fusion and allows lower processing temperatures. Copolymers are used in flooring and coatings. This copolymer sometimes contains maleic add or vinyl alcohol (hydrolyzed from the poly(vinyl acetate ) to improve the coating s adhesion to other materials, including metals, Copolymers with vinylidene chloride are used as barrier films and coatings. Copolymers of vinyl chlonde with acrylic esters in latex from are used as film formers in paint, nonwoven fabric binders, adhesives, and coatings. Copolymers with olefins improve thermal stability and melt flow, but at some loss of heat-deflection temperature,... 

Processing with the styrene monomer requires that precautions have to be taken to ensure the proper removal and handling of this toxic material. Legal limits in the workplace have been set up by regulations. Other monomers used include diallyl phthlate (DAP), para-methylstyrene (PMS), vinyl acetate (VA), vinyl toluene (VT), adding paraffin wax, and styrene suppressant additive. Suppliers and fabricators continue to target in the reduction of styrene monomer quickly, effectively, and economically. A wide variation in properties can be obtained by changes in polyester formulation. 

PAN, a synthetic fiber, is a polymer of acrylonitrile monomers. Worldwide, 2.73 million tons of PAN are produced per year, of which over 98% are processed as filament yarn serving as material in the textile industry (Tauber et al., 2000). PAN usually has a molecular weight of 55,000-70,000 g mol and is most commonly a copolymer produced by radical polymerization from acrylonitrile, 5-10 mol% vinyl acetate (or similar nonionic comonomers) to disrupt the regularity and crystallinity, and ionic comonomers, such as sulfuric or sulfonic acid salts. PAN is a hydrophobic polymer that affects the processability of the fibers. The surface is not easily wetted. 

High-Temperature Application. Vinyl Acetate Distribution in Copoly (ethylene-vinyl acetate). In the characterization of polymers, molecular distribution and composition are two critical parameters. Every physical property and processing change of the material can be related to these two parameters. With copolymers, IR spectroscopy can be used for determination of the distribution of one or both monomers within the molecular weight distribution. 

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