Acrylates BASF synthesis

Monomer syntheses and their industrial polymerization and copolymerization were initiated in the thirties by IG Farbenindustrie, now BASF, and this company is still the main producer. Other companies, as GAF Corporation and Union Carbide in the United States or ICI in the United Kingdom came on the market at a later time. Actually BASF is the only producer of homopolymers, whereas copolymers are manufactured by BASF and GAF Co. We shall not consider here the synthesis of the industrial copolymers of methylvinyl ether and maleic anhydride (Gantrez-GAF, Sokalan-BASF), of isobutylvinyl ether and vinyl chloride (Laroflex MP 15-60, BASF), and of isobutylvinyl ether and acrylic monomers (Acro-nal, BASF) as they are produced by radical copolymerization. 

The synthesis of carboxylic acids by carbonylation of unsaturated hydrocarbons or alcohols was developed mainly by Reppe and his co-workers in the laboratories of BASF at Ludwigshafen. Many industrially important processes such as the synthesis of acrylic acid, propionic acid, and acetic acid were elaborated there in the period from the late 1930s to the mid-1950s [1, 2]. Reppe s introduction of metal carbonyls as catalysts for carbonylation reactions was of paramount importance and many processes, which are still industrially relevant today, were developed rapidly (eq. (1), [3]). 

Beilstein Handbook Reference) Acrylic acid butyl ester Acrylic acid n-butyl ester AI3-15739 BRN 1749970 Butyl 2-propenoate Butyl acrylate Butylester kyseliny akrylove CCRIS 3401 EINECS 205-480-7 HSDB 305 NSC 5163 UN2348. Intermediate in organic synthesis, polymers and copolymers for solvent coatings, adhesives, paints, binders, emulsifiers. Liquid mp = -54.6° bp = 145° d = 0.8898 Am n 242 nm (isooctane) insoluble in H2O, slightly soluble in CCU, soluble in EtOH, Et20, Me2CO LDso (rat orl) = 3,73 g/kg. BASF Corp. 

Walter Reppe also used his new base to expand the chemistry of acetylene. His first major breakthrough, in the summer of 1939, was the addition of carbon monoxide to acetylene in the presence of alcohols (or water) and a nickel catalyst to form acrylates. Carbon monoxide had attracted attention for many years as a readily available, cheap and reactive carbon compound. I.G. Farben employed it in the Pier methanol synthesis, Ruhrchemie used it in the Fischer-Tropsch synthetic petrol process, and Du Pont had carried out research on the addition of carbon monoxide to olefins at very high pressure and temperatures. Additional impetus for the use of carbon monoxide in acetylene chemistry was provided by the introduction of covered carbide furnaces at I.G. Farben s Knapsack plant in 1938, which permitted the collection of by-product carbon monoxide. The polymers of acrylic esters were already used for treating leather and for paint, but acrylic acid was made from ethylene oxide, and consequently was rather expensive. Reppe s process reached the pilot plant stage by 1945, and was subsequently used on a large scale by BASF and its American partners. 

Actual operating capacities of Reppe carbonylation processes are difficult to estimate since only a few data are available in the literature. However, it is known that some of the syntheses are carried out on an industrial scale, e. g. the synthesis of acrylates from acetylene, carbon monoxide and alcohols (BASF) [1004, 1005], the acetic acid synthesis from methanol and carbon monoxide and the synthesis of higher molecular weight saturated carboxylic acids from olefins, carbon monoxide and water. Propionic acid (30,000 tons/year) and to a smaller extent heptadecanoic dicarboxylic acid are manufactured via the carbonylation route at BASF. Butanol is made from propylene in Japan [1003, 1004]. 

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