Acrylic acid commercial development

A significant step towards commercial success came with a discovery in the late 1950s by E. Ulrich at 3M when he found that copolymerization of hydrogen bonding monomers, like acrylic acid with alkyl acrylates resulted in cohesively strong, yet tacky materials [63]. Since then, newer developments in such areas as polymer crosslinking, and the synthesis and copolymerization of new monomers, have led to a rapid penetration of acrylics throughout the PSA industry. 

A variety of ionomers have been described in the research literature, including copolymers of a) styrene with acrylic acid, b) ethyl acrylate with methacrylic acid, and (c) ethylene with methacrylic acid. A relatively recent development has been that of fluorinated sulfonate ionomers known as Nafions, a trade name of the Du Pont company. These ionomers have the general structure illustrated (10.1) and are used commercially as membranes. These ionomers are made by copolymerisation of the hydrocarbon or fluorocarbon monomers with minor amounts of the appropriate acid or ester. Copolymerisation is followed by either neutralisation or hydrolysis with a base, a process that may be carried out either in solution or in the melt. 

Theses polymers are made from acrylic acid, its homologues and their derivatives. Glass like resins were made from esters of aerylic acid in 1877 by Fitting and Peter by Kahlbaum. In 1928, Rohm and Hass, a German Company started commercial development of methacrylic esters. Limited production started in 1933. The rapidly expanding air-force used this plastic in place of glass in the aeroplanes. Most of the early production of "Plexiglass was used up by air-force planes. In 1936, ICI marketed methyl methacrylate sheets as "Perspex". 

An anesthetic drug, Richlocaine, developed jointly by scientists from Kazakhstan and Russia, and commercially available biologically active substances bovine serum albumin, lysozyme, and catalase were used. Hydrogels of acrylamide and acrylic acid copolymer(AA-AAc),poly(N-isopropylacrylamide)(PNIPA),N-isopropylacrylamide and acrylic acid copolymer (NlPA-AAc), N-isopropylacrylamide and 2-(acrylamido)-2-propanesulfonic acid copolymer (NIPA-APSA) were synthesized. Diffusion parameters of bioactive substances into hydrogel matrices were calculated using Eq. (19.1) ... 

Acrolein and Acrylic Acid. Acrolein and acrylic acid are manufactured by the direct catalytic air oxidation of propylene. In a related process called ammoxida-tion, heterogeneous oxidation of propylene by oxygen in the presence of ammonia yields acrylonitrile (see Section 9.5.3). Similar catalysts based mainly on metal oxides of Mo and Sb are used in all three transformations. A wide array of single-phase systems such as bismuth molybdate or uranyl antimonate and multicomponent catalysts, such as iron oxide-antimony oxide or bismuth oxide-molybdenum oxide with other metal ions (Ce, Co, Ni), may be employed.939 The first commercial process to produce acrolein through the oxidation of propylene, however, was developed by Shell applying cuprous oxide on Si-C catalyst in the presence of I2 promoter. 

In the 1930s, the Reppe group developed commercial processes for the production of carboxylic acids and esters by the carbonylation of alkynes and alkenes using metal carbonyls [4], In particular, an industrial process for producing acrylic acid or ester by the carbonylation of highly explosive acetylene, catalysed by extremely toxic Ni(CO)4, was established (eq. 1.3). 

Commercial production of acetic acid has been revolutionized in the decade 1978—1988. Butane—naphtha liquid-phase catalytic oxidation has declined precipitously as methanol [67-56-1] or methyl acetate [79-20-9] carbonylation has become the technology of choice in the wodd market. By-product acetic acid recovery in other hydrocarbon oxidations, eg, in xylene oxidation to terephthalic acid and propylene conversion to acrylic acid, has also grown. Production trom synthesis gas is increasing and the development of alternative raw materials is under serious consideration following widespread dislocations in the cost of raw material (see Chemurgy). 

In 1957 Standard Oil of Ohio (Sohio) discovered bismuth molybdate catalysts capable of producing high yields of acrolein at high propylene conversions (>90%) and at low pressures (12). Over the next 30 years much industrial and academic research and development was devoted to improving these catalysts, which are used in the production processes for acrolein, acrylic acid, and acrylonitrile. All commercial acrolein manufacturing processes known today are based on propylene oxidation and use bismuth molybdate based catalysts. 

Other Syntheses. Acrylic acid and other unsaturated compounds can also be made by a number of classical elimination reactions. Acrylates have been obtained from the thermal dehydration of hydracrylic acid (3-hydroxypropanoic acid [503-66-2]) (84), from the dehydrohalogenation of 3-halopropionic acid derivatives (85), and from the reduction of dilaalopropionates (2). These studies, together with the related characterization and chemical investigations, contributed significantly to the development of commercial orgaioic chemistry. 

Historically, the development of the acrylates proceeded slowly they first received seiious attention from Otto Rohm. Acrylic acid (propenoic acid) was first prepared by the ah oxidation of acrolein in 1843 (1,2). Methyl and ethyl acrylate were prepared in 1873, but were not observed to polymerize at that time (3). In 1880 poly(metliyl acrylate) was reported by G. W. A. Kahlbaum, who noted that on dry distillation up to 320°C the polymer did not depolymerize (4). Rohm observed the remarkable properties of acrylic polymers while preparing for his doctoral dissertation in 1901 however, a quarter of a century elapsed before he was able to translate his observations into commercial reality. He obtained a U.S. patent on the sulfur vulcanization of acrylates in 1912 (5). Based on the continuing work in Robin s laboratory, the first limited production of acrylates began in 1927 by the Rohm and Haas Company in Darmstadt, Germany (6). Use of this class of compounds has grown from that time to a total U.S. consumption in 1989 of approximately 400,000 metric tons. Total worldwide consumption is probably twice that. 

The production of carboxylic acids via carbonylation catalysis is the second most important industrial homogeneous group of processes. Reppe developed most of the basic carbonylation chemistry in the 1930s and 1940s. The first commercial carbonylation process was the stoichiometric Ni(CO)4-based hydroxycarbonylation of acetylene to give acrylic acid (see Section 3.5 for details). This discovery has since evolved into a trae Ni-catalyzed process, used mainly by BASF. The introduction of rhodium catalysts in the 1970s revolutionized carboxylic acid production, particularly for acetic acid, much in the same way that Rh/PPhs catalysts changed the importance of hydroformylation catalysis. 

Subsequently D Alello developed the polystyrene-hased resin in 1944 (4). Two years later, polystyrene anion-exchange resins made hy chloromethylation and amination of the matrix were produced. Four principal classes of ion-exchange resins were commercially availahle by the 1950s. These are the strong-acid, strong-hase, and weak-hase resins derived from styrene-divinylbenzene copolymers, and the weak-acid resins derived from cross-linked acrylics. To this day, the most widely used ion exchangers are synthetic organic polymer resins based on styrene- or acrylic-acid-type monomers as described by D Alelio in U.S. Patent 2,3666,007. 

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