Rohm, Otto

POLYMER MILESTONES—OTTO ROHM OTTO HAAS... 

Historically, the development of the acrylates proceeded slowly they first received serious attention from Otto Rohm. AcryUc acid (propenoic acid) was first prepared by the air 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(methyl 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 acryUc 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 reaUty. He obtained a U.S. patent on the sulfur vulcanization of acrylates in 1912 (5). Based on the continuing work in Rohm 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. 

In 1901 Otto Rohm reported on his studies of acrylic polymers for his doctoral dissertation. His interest in these materials, however, did not cease at this stage and eventually in 1927 the Rohm and Hass concern at Darmstadt, Germany commenced limited production of poly(methyl acrylate) under the trade names... 

Acknowledgement The author thanks the Deutsche Forschungsgemeinschaft, the Fonds der Chemi-schen Industrie and the Dr. Otto Rohm Gedachtnisstiftung for their support of these investigations. 

Rolf Miilhaupt for his generous support, the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie, the Otto-Rohm-Gedachtnisstiftung and Bayer AG for financial support. 

Tauber, H. (1949) The Chemistry and Technology of Enzymes. New York Wiley. Trommsdorf, E. (1976) Dr. Otto Rohm—Chemiker und Unternehmer. Diisseldorf Econ. Turner, M. (1994) Biological catalysis and biotechnology. In The Chemical Industry, edited by A.Heaton, 2nd ed., pp. 306-372. Blackie Academic and Professional. Ullmaim, F. (1914) Enzyklopadie der technischen Chemie, Vol 5, p. 445. Berlin Urban und Schwarzenberg. 

At a considerably later date. Frankland prepared ethyl methacrylate and methacrylic acid from ethyl a-hydroxyisobutyrate and phosphorus trichloride. Tollen prepared aciylate esters from 2,3-dibromopropionate esters and zinc. Otto Rohm, in 1901. described the structures of the liquid condensation products (including dimers and timers) obtained from the action of sodium alkoxides on methyl and ethyl acrylate. Shortly after World War 1, Rohm introduced a new acrylate synthesis, noting that an acrylate is formed in good yield from heating ethylene cyanohydrin and sulfuric acid and alcohol. A major incentive for the development of a clear, tough plastic acrylate was for use in the manufacture of safety glass. 

Otto Rohm Darmstadt, Germany Patent for enzymatic treatment of leather (with trypsin)... 

The application of enzymes, however, is not novel already in 1913, Otto Rohm, founder of what would become the chemical giant Rohm and Haas, had added a proteolytic enzyme, mainly trypsin, from milled animal pancreas and dog waste to detergents. Marketed in Germany in 1914 as Burnus , this innovation was way ahead of its time and ran into several problems First, the very crude proteolytic enzyme contained many impurities which sometimes stained the very textile it was supposed to clean. Second, one tablet could be added to 10 liters of water to remove stains from clothes. Unfortunately, consumers were used to bulky washing powders which lathered a lot, and they did not believe that such a small tablet could work. Third, the process of enzyme extraction was not economical enough to include it in routine household detergents. 

Acknowledgements. Financial support of the author s work by the Deutsche Forschungsgemein-schaft, the Fonds der Chemischen Industrie and Dr. Otto Rohm-Gedachtnisstiftung is gratefully acknowledged. 

A German scientist, Otto Rohm, was the first to patent the use of enzymes in laundry in 1913 [91] but it was not until 1930 that the use of pancreatic enzymes in presoak solutions became popular in the detergent industry. However the application of peroxidases in laundry to prevent back staining is very recent. A peroxidase-based system for the inhibition of dye transfer during washing with laundry... 

Otto Rohm (top) and Otto Haas (bottom) (Courtesy Rohm and Haas Company). 

Proteases were first introduced as a detergent product in 1931 by the German scientist Otto Rohm. This product was essentially a mixture of animal pancreatic enzymes including trypsin and chymotrypsin. It was not very effective, as these enzymes lack broad substrate specificity and do not exhibit high activity or stability at alkaline pH. 

Although acrylic acid was first synthesized in 1843 and polymerized in 1847, the properties of deriyed monomers and polymers were not extensiyely investigated until the classic work of Otto Rohm, beginning in 1901. The first general synthetic process for manufacturing acrylic esters was accomplished in 1927 in Germany and was based on the reactions... 

PMMA was first synthesized in 1928 in the laboratories of the German chemical firm Rohm and Haas. After five years of research, one of the firm s founders, Otto Rohm, found a way of manufacturing sheets of polymethylmethacrylate. He patented his invention and the company was soon producing the... 

Acknowledgements. Financial support has been obtained by the Deutsche Forschungsgemein-schaft, the Fonds der Chemischen Industrie and the Otto Rohm Stiftung. We would like to express our most sincere thanks to the many collaborators whose names appear in the References, for their contributions. We are grateful to Profs. H. Bock and W. von Niessen for the communication of results prior to publication. 

Sponsorship of this work by the Deutsche Forschungsgemeinschaft, Verband der Chemischen Industrie e.V., and Otto-Rohm-Stiftung is gratefully acknowledged. A. B. thanks the Studienstiftung des Deutschen Volkes and the Verband der Chemischen... 

The authors wish to thank Dr. W. Siemens and Dr. B. Schriewer. The results of the calorimetric and electron microscopic investigations are taken from their Ph.D. theses. They thank Rohm GmbH, Darmstadt, for gifts and characterization of PMMA-samples. They are indebted to Deutsche Forschungsgemeinschaft, Verband der Chemischen Industrie— Fonds der Chemie and Dr. Otto Rohm-Gedachtnisstiftung for financial support of this work. 

Frankland and Duma first reported methacrylic acid in 1865 (3). However, like acrylic acid, its commercial development came many years later in 1933 (4). The development required pioneering chemistry on the monomer and its derivatives by Dr. Otto Rohm pubhshed in his doctoral thesis in 1901 and its evolution through the formation of the Rohm and Haas Co. in 1909 (5-8). Like the acrylic acid, methacrylic acid and its vinyl derivatives are used mainly in the preparation of polymers. There is httle interest in small organic molecules based on the monomers. 

The usage of acrylic esters as building blocks for polymers of industrial importance began in earnest with the experimentation of Otto Rohm (1). The first recorded preparation of the basic building block for acrylic ester polymers, acrylic acid, took place in 1843 this synthesis relied on the air oxidation of acrolein (2,3). The first acrylic acid derivatives to be made were methyl acrylate and ethyl acrylate. Although these two monomers were synthesized in 1873, their utility in the polymer area was not discovered until 1880 when Kahlbaum polymerized methyl acrylate and tested its thermal stability. To his surprise, the polymerized methyl acrylate did not depolymerize at temperatures up to 320°C (4). Despite this finding of incredibly high thermal stability, the industrial production of acrylic ester polymers did not take place for almost another 50 years. 

The commercial discovery of acrylic ester polymers took place while Otto Rohm was conducting his doctoral research in 1901. Rohm obtained a U.S. patent in 1912 covering the vulcanization of acrylates with sulfur (5). Commercial production of acrylic ester polymers by the Rohm and Haas Co. of Darmstadt, Germany, commenced in 1927 (6). 

However, this part of the story illustrates that the concepts developed by H. S. had the strongest impact on research and development in industry and led to revolutionary activities in the production of polymer-based materials. Among others, Wallace H. Carothers was a careful reader of Staudinger s publications [1, 2]. The two scientists actually met once in 1937 [2] and seemed to have understood each other very well. Another record describing the tremendous impact and response of the cOTicepts of H. S. on industrial developments is to be found in the book by Ernst Trommsdorff [ 11 ] on the achievements of Otto Rohm, the founder of Rohm and Haas Company. This company did significant work in the industrial development of acrylate chemistry and materials based on this chemistry, all as a consequence of applying the ideas of H. S. 

Trommsdorff E (1976) Dr. Otto Rohm Chemiker und Untemehmer. Econ, Diisseldorf... 

At about the same time Otto Rohm, a German American, made the first acrylic resin, polymethylmethacrylate, known as Plexiglas or Perspex ... 

Otto Rohm is credited with the development of perhaps the most widely used polymer in orthopaedic surgery— poly(methylmethacrylate) (PMMA)—in 1901 [1] but the material did not come into widespread use in orthopaedics until Sir John Chamley described its use for bonding prostheses to bone in the early 1960s [2]. A good review of the early work in characterizing PMMA including the evolution of the use in orthopaedics can be found in the article by Dennis Smith where he describes his collaboration with Chamley [3]. 

Another class of industrially important polymers, polyacrylates and methacrylates, is associated with the firm of Rohm and Haas. Otto Rohm (1876-1939) was both a highly trained organic polymer chemist and a great industrialist. In 1907 he teamed with Otto Haas (1872-1960) to found both a successful German and American Company (Fig. 3.9). I owe a personal debt of gratimde to Otto Haas s son, John. He endowed the Charles Price Fellowship in Polymer History at the Chemical Heritage Foundation. 

Fig. 3.9 Otto Rohm and Otto Haas (Rohm and Haas, by permission)...

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