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Hermann Staudinger

Hermann Staudinger

Lived 1881 – 1965.

Hermann Staudinger brought about a revolution in our understanding of chemistry, establishing that molecules made of hundreds of thousands of atoms exist: he described them as high polymers or macromolecules, stating that starch, cellulose, and proteins are examples of natural macromolecules.

Today we know that a single DNA molecule contains many billions of atoms. Molecules this big could not be envisaged until Staudinger triggered a paradigm shift.

Staudinger was the sole recipient of the 1953 Nobel Prize in Chemistry for his breakthroughs in macromolecular chemistry.

In addition to his Nobel Prize winning work, Staudinger made several important discoveries in organic chemistry.

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Achievements and Key Points

Some of Hermann Staudinger’s major achievements, often supported by different students and coworkers, were:

  • The discovery of ketenes.
  • The discovery that chrysanthemum flowers produce natural insecticides called pyrethroids. Today these products are used as household insecticides: they are biodegradable and have very low toxicity to mammals.
  • Several discoveries in organophosophus chemistry, such as the Staudinger reduction converting azides to amines.
  • The discovery of polyoxymethylene, a polymer which later became an important commercial plastic.
  • Establishing that many natural and synthetic substances are made of enormous, covalently bonded polymer chains.
  • Establishing the similarity between polymers produced in nature and those produced in the laboratory.
  • Demonstrating that synthetic polymers can make fibers similar to natural fibers.
  • Founding the world’s first academic journal devoted to macromolecules.

Beginnings

Hermann Staudinger was born on March 23, 1881 in the German city of Worms. He was one of four children in a relatively prosperous, well-educated family.

His father was Franz Staudinger, a grammar school teacher, philosopher, and socialist. His mother was Auguste Wenck, active in campaigning for women’s rights.

Education

In addition to a traditional academic education, Hermann trained in carpentry: his father wanted Hermann to understand manual work.

In 1899, at age 18, Hermann graduated from the Grand Ducal High School (now known as the Rudi-Stephan-Gymnasium) in Worms. A lover of the natural world, he planned to study botany at college, but one of his teachers persuaded him to study chemistry instead, arguing that all biology was based on chemistry.

Four years later, in 1903, Hermann Staudinger graduated from the University of Halle with a doctorate in chemistry for his investigations of organic chemical reactions – his thesis title was: The addition of malonic ester to unsaturated compounds.

Career Summary

  • In 1903, Staudinger moved to the University of Strasbourg to carry out postdoctoral research as an organic chemist. In 1905, he discovered diphenylketene, the first ketene. In spring 1907, age 26, he qualified as a university lecturer by passing further examinations.
  • In 1907, Staudinger became an assistant professor of chemistry at Karlsruhe’s Technical High School.
  • In 1912, age 31, he moved to Switzerland as Chair of General Chemistry at the Technical High School of Zurich. Here he began diverting his research focus away from classical organic chemistry into macromolecules. Nobody knew if macromolecules actually existed.
  • In 1914, when World War 1 broke out, Staudinger did not return to Germany. As a pacifist, he refused to carry out war-related research work for Germany.
  • In 1926, he returned to Germany as director of the Chemical Laboratory at the University of Freiburg. Some of the faculty opposed his appointment, objecting to his pacifism in World War 1.
  • In 1940, he founded Freiburg’s Institute of Macromolecular Chemistry.
  • In 1943, he founded the first journal of polymer chemistry, Journal für Makromolekulare Chemie, which in 1947 became Die Makromolekulare Chemie – now Macromolecular Chemistry and Physics.
  • Staudinger remained at Freiburg for the rest of his career, retiring officially in 1951, age 70, but continuing as director of the Institute for Macromolecular Chemistry for a further five years.

Hermann Staudinger and Macromolecules

Before Staudinger

The idea that small, unsaturated molecules could react together to create larger molecular chains was not Staudinger’s.

ethene

Ethylene (or ethene) is an unsaturated molecule
– i.e. it has a double bond.

In 1863, Marcellin Berthelot used the word ‘polymer’ to describe larger chains formed by the reaction of smaller molecules and proposed the general principle that unsaturated compounds could react with one another to form polymers.

Two molecules of ethene react to form butane.

Two molecules of ethene react, doubling the length of the carbon chain from 2 to 4 atoms.

In 1869, Berthelot described his polymerization experiments on molecules such as ethene, propene, and pentene. Starting with these lower boiling point hydrocarbons, and using a catalyst such as sulfuric acid to push the reaction along, he produced higher boiling point hydrocarbons.

Starting with ethylene, whose boiling point is −103.7 °C, Berthelot produced a mixture of hydrocarbons with a boiling range of 280-300 °C. This boiling range indicated the products had about 16 carbons per molecule compared with ethylene’s 2 carbons per molecule. Berthelot described his product as polyethylene.

ethene reacts to form hexadecane

Berthelot’s early experiments showed it was possible to increase the length of the carbon chain from 2 to 16, with an average of 8 ethylene molecules reacting to form a larger hydrocarbon molecule.

C16

Berthelot’s 16-carbon chain molecule drawn in full.

Later workers found they could produce higher molecular weight hydrocarbons with longer chains.

ethylene forms polyethylene

Reaction conditions can be found so that n is a large number and the product is polyethylene.

Staudinger Champions the Macromolecule

In 1920, in his famous paper Über Polymerisation, Staudinger stated that substances such as polystyrene, polyvinylchlorides, and rubber, were composed of polymer chains with very high molecular weights. Each chain in these ‘high polymers’ could contain over 100,000 atoms – these were huge molecules. He said the bonds within these chains were exclusively covalent.

The scientific consensus at the time was that Staudinger’s claims of 100,000 atoms in polymer chains were absurd. His many opponents said the behavior of ‘high polymers’ was explained by short polymer chains associating with one another as colloids.

In 1922, Staudinger coined the word macromolecule to describe natural, long-chained polymeric substances such as rubber, cellulose, and proteins.

A Discouraging Start at Freiburg

While Staudinger promoted the concept of macromolecules, most chemists continued to believe it was impossible for such molecules to exist.

When Staudinger took over at Freiberg in 1926, the previous director, Heinrich Otto Wieland, soon to be awarded the Nobel Prize in Chemistry (1927), told him:

Heinrich Otto Wieland“Dear colleague, abandon your idea of large molecules; organic molecules with molecular weights exceeding 5,000 do not exist. Purify your products such as rubber, they will crystallize and turn out to be low molecular weight compounds.”

Heinrich Otto Wieland
Communication to Staudinger, 1926
 

Staudinger Pushes Forward

At Freiburg, Staudinger focused all his energy on polymers. The tide began to turn in his favor as chemists increasingly saw that Staudinger’s experimental evidence and their own experimental results were better explained by the existence of high molecular weight polymers than the behavior of colloids of low molecular weight polymers.

Staudinger’s discovery of polyoxymethylene and his proof in 1927 that its crystallographic unit cell was much smaller than its polymer chain were crucial milestones.

In 1927, Staudinger and Gustav Mie proved that polymers made in the laboratory could yield fibers similar to natural fibers. Until then scientists believed that only Nature in the shape of plants (e.g. cotton and flax) and animals (e.g. wool and silk) could make fibers. Staudinger’s discovery paved the way for the discovery of nylon – the first synthetic fiber – by Wallace Carothers in 1935.

Hermann Staudinger“The only difference between macromolecules and the small molecules of low molecular substances is one of structural size.”

Hermann Staudinger
Nobel Lecture, 1953
 

Synthetic Macromolecules

A macromolecule, also often known as a polymer molecule, is made by linking together molecules of smaller substances into a long, chemically bonded chain. For example, styrene molecules can react together to form polystyrene, as shown below.

A Polymerization Reaction

styrene-polystyrene

Large numbers of individual styrene molecules on the left react together in a polymerization reaction to form giant chain molecules of polystyrene on the right.

No Macromolecules, No Life, No Information Age

A macromolecule:

  • may be a natural molecule – for example DNA or protein. All life on Earth is based on natural macromolecules.

or

  • may be a synthetic molecule – for example nylon or polypropylene. Without synthetic macromolecules there would be no laptops, smartphones, monitors, computers, televisions, speakers, credit cards, cars, etc. Our modern information age is possible only by virtue of synthetic macromolecules.

Staudinger in Nazi Germany

In 1933, Adolf Hitler became Germany’s leader, and Germans with Jewish ancestry began to be fired from their jobs. Other Germans who were suspected of being unsympathetic to Nazi ideals also faced dismissal.

Staudinger’s pacifism in World War 1 made him a prime target for Nazi misgivings. He was investigated and interrogated by the Gestapo. His brother, a Social Democrat politician was arrested, but escaped to America where he became an economics professor.

Following an investigation, Staudinger was allowed to continue as director of Freiburg’s Chemical Laboratory, but only after he signed an undated letter of resignation. In 1937, he was prohibited from leaving Germany.

Although Jews were dismissed from his university, Staudinger did not protest. Indeed, it emerged long after his death that by 1936 he was expressing the view that too many non-Aryans were being allowed to study at Freiburg. In 1942, he wrote to the university’s rector observing that with Jews now absent from Germany’s universities, there were too many part-Jews present. On the other hand, Staudinger seems to have gone out of his way to treat individual Jews and part-Jews in his own department as fairly as possible.

Like many Germans of that era, Staudinger seems to have cozied up to the Nazis as a career move. At the end of the war, and during his lifetime, he was not considered to have been a Nazi collaborator. In recent years his role has been regarded more ambiguously.

Nobel Prize

In 1953, Staudinger was the sole recipient of the Nobel Prize in Chemistry for:

“his discoveries in the field of macromolecular chemistry.”

Other Honors

1930: Emil Fischer Medal, awarded once every two years for outstanding work in organic chemistry.
1952: German Order of Merit.
1954: Honorary Citizen of Freiburg.

Family and the End

In 1906, age 25, Staudinger married Dorothea Förster. They had four children: Eva, Hilde, Hansjürgen, and Klara.

In the 1920s, the couple’s interests diverged: Staudinger was passionate about scientific research and Dorothea was passionate about changing society by starting up not-for-profit cooperative supermarkets. Staudinger and Dorothea divorced after 21 years of marriage in 1925. The following year, Staudinger moved back to Germany to the University of Freiburg. Dora and the children (ages 11 – 19) remained in Switzerland. After the divorce Staudinger stayed in touch and on good terms with his family.

In 1927, age 46, Staudinger married 25-year-old Magda Woit, a Ph.D. qualified Latvian biologist who spoke English, French, German, and Russian fluently, and was a talented pianist and violinist.

Magda became Staudinger’s long-term collaborator in studies of biological macromolecules.

Hermann Staudinger died age 84 on September 8, 1965 in Freiburg and was buried in the Freiburg Cemetery. He was survived by Magda, who died in 1997, age 94. She was buried next to her husband. Staudinger was also survived by his four children and his first wife, Dorothea.

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Further Reading
Frank M. McMillan
The Chain Straighteners: Fruitful Innovation : the Discovery of Linear and Stereoregular Synthetic Polymers
Springer, June 1979

Bernd Martin
Die Entlassung der jüdischen Lehrkräfte an der Freiburger Universitüt und die Bemühungen um ihre Wiedereingliederung nach 1945
Schicksale : jüdische Gelehrte an der Universität Freiburg in der NS-Zeit. Freiburg: Rombach, 1995. (Freiburger Universitätsblätter ; 129 = 34. Jg. 1995), S. 7 – 46

F.B. Seymour
Pioneers in Polymer Science
Springer Science & Business Media, Dec 2012

Urs Ruegg
Foreword: Memories of Hermann Staudinger by one of his grandchildren.
Advances in Polymer Science. 262. V-X, 2013

Hans-Joachim Cantow and Rolf Mülhaupt
Hermann Staudinger and Polymer Research in Freiburg
Adv Polym Sci., 261: pp 21–38, 2013

Virgil Percec
Hierarchical Macromolecular Structures: 60 Years after the Staudinger Nobel Prize
Springer, July 2014

Creative Commons
Image of Staudinger courtesy of ETH-Bibliothek Zürich, Bildarchiv under the Creative Commons Attribution-Share Alike 3.0 Unported license.

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