Karl Ziegler

Karl Waldemar Ziegler (German: [kaːʁl ˈvaldəˌmaʁ

ˈt͡siːɡlɐ]; 26 November 1898 – 12 August 1973) was a Karl Ziegler
German chemist who won the Nobel Prize in
Chemistry in 1963, with Giulio Natta, for work on
polymers. The Nobel Committee recognized his
"excellent work on organometallic compounds
[which]...led to new polymerization reactions and ...
paved the way for new and highly useful industrial
processes".[1] He is also known for his work involving
free-radicals, many-membered rings, and
organometallic compounds, as well as the development
of Ziegler–Natta catalyst. One of many awards Ziegler
received was the Werner von Siemens Ring in 1960
jointly with Otto Bayer and Walter Reppe, for
expanding the scientific knowledge of and the Karl Ziegler
technical development of new synthetic materials.[2] Born Karl Waldemar Ziegler
26 November 1898
Helsa near Kassel, German
Biography Empire
Died 12 August 1973 (aged 74)
Mülheim, West Germany
Early life and education Nationality German
Karl Ziegler was born on 26 November 1898 in Helsa Alma mater University of Marburg
near Kassel, Germany and was the second son of Karl Known for Ziegler process
Ziegler, a Lutheran minister, and Luise Rall Ziegler.[3] Ziegler–Natta catalyst
He attended Kassel-Bettenhausen in elementary Wohl–Ziegler bromination
school. An introductory physics textbook first sparked Thorpe–Ziegler reaction
Ziegler's interest in science. It drove him to perform Dienone–phenol rearrangement
experiments in his home and to read extensively Organoaluminium chemistry
beyond his high school curriculum. He was also Organolithium reagent
introduced to many notable individuals through his Synthesis of ascaridole
father, including Emil Adolf von Behring, recognized
Awards Liebig Medal (1935)
for the diphtheria vaccine.[4] His extra study and
War Merit Cross 2nd Class (1940)
experimentation help explain why he received an
Werner von Siemens Ring (1961)
award for most outstanding student in his final year at
Nobel Prize for Chemistry (1963)
high school in Kassel, Germany.[4] He studied at the
Pour le Mérite (1969)
University of Marburg and was able to omit his first
FRS (1971)
two semesters of study due to his extensive
background knowledge. His studies were interrupted Scientific career
however, as during 1918 he was deployed to the front Fields Organic chemistry
as a soldier to serve in World War I.[5] He received his Institutions Goethe University Frankfurt
Ph.D. in 1920, studying under Karl von Auwers.[3] His University of Heidelberg
dissertation was on "Studies on semibenzole and University of Halle-Saale
related compunds" which led to three publications.[5] Max Planck Institute für
Kohlenforschung
University of Chicago
Career
Doctoral Karl von Auwers
Karl Ziegler showed an eagerness for science at an advisor
early age. He progressed through schooling quickly
receiving a doctorate from the University of Marburg in 1920. Soon after, he briefly lectured at the
University of Marburg and the University of Frankfurt.

In 1926 he became a professor at the University of Heidelberg where he spent the next ten years
researching new advances in organic chemistry.[6][7] He investigated the stability of radicals on trivalent
carbons leading him to study organometallic compounds and their application in his research. He also
worked on the syntheses of multi-membered ring systems.[7] In 1933 Ziegler published his first major
work on large ring systems, "Vielgliedrige Ringsysteme" which presented the fundamentals for the
Ruggli-Ziegler dilution principle.[8]

In 1936 he became Professor and Director of the Chemical Institute

(Chemisches Institut) at the University of Halle-Saale and was also a
visiting lecturer at the University of Chicago.[7] Ziegler, who was a
Patron Member of the SS[9] received the War Merit Cross 2nd Class
in October 1940.[10]

From 1943 until 1969, Ziegler was the Director of the Max Planck
Institute for Coal Research (Max-Planck-Institut fur
Kohlenforschung) formerly known as the Kaiser-Wilhelm Institute Max Planck Institute for Coal
Research.
for Coal Research (Kaiser-Wilhelm-Institut fur Kohlenforschung) in
Mülheim an der Ruhr as a successor to Franz Fischer.[8]

Karl Ziegler was credited with much of the postwar resurrection of chemical research in Germany and
helped found the German Chemical Society (Gesellschaft Deutscher Chemiker) in 1949. He served as
president for five years.[7][11] He was also the president of the German Society for Petroleum Science and
Coal Chemistry (Deutsche Gesellschaft für Mineralölwissenschaft und Kohlechemie), from 1954 to
1957.[7] In 1971, The Royal Society, London, elected him as a Foreign Member.[7]

Personal life
In 1922, Ziegler married Maria Kurtz.[2] They had two children, Erhart and Marianna.[3] His daughter,
Dr. Marianna Ziegler Witte was a doctor of medicine and married a chief physical of a children's hospital
(at that time) in the Ruhr. His son, Dr. Erhart Ziegler, became a physicist and patent attorney. In addition
to his children, Karl Ziegler has five grandchildren by his daughter, and five by his son.[1] At least one of
his grandchildren, Cordula Witte, attended his Nobel Prize reception as there is a picture of the two of
them happily dancing.[5] Ziegler enjoyed traveling around the world with his family, especially on
cruises. He even charted special cruises and airplanes for eclipse viewing. It was during a 1972 eclipse-
viewing cruise with his grandson that Karl Ziegler became ill. He died a year later.[6]
Ziegler and his wife were great lovers of the arts, particularly paintings. Karl and Maria would present
each other with paintings for birthdays, Christmases, and anniversaries. They amassed a large collection
of paintings, not necessarily of one particular period, but of paintings they enjoyed. Maria, being an avid
gardener, particularly enjoyed flower paintings by Emil Nolde, Erich Heckel, Oskar Kokoschka, and Karl
Schmidt-Rottluff. Karl enjoyed pictures of the places that he and his wife called home, including pictures
of Halle and the Ruhr valley. Forty-two images from their shared collection were incorporated into a
foundation, bequeathed to the Mülheim Ziegler Art Museum.[12]

As a man of many discoveries, Karl Ziegler was also a man of many patents. As a result of his patent
agreement with the Max Planck Institute, Ziegler was a wealthy man. With part of this wealth, he set up
the Ziegler Fund with some 40 million deutsche marks to support the institute's research.[6] Another
namesake is the Karl-Ziegler-Schule, an urban high school that was founded on 4 December 1974,
renaming a previously existing school. The school is located in Mülheim, Germany.[12]

Karl Ziegler died in Mülheim, Germany on 12 August 1973; his wife died in 1980.

Scientific advancements
Throughout his life, Ziegler was a zealous advocate for the necessary indivisibility of all kinds of
research. Because of this, his scientific achievements range from the fundamental to the most practical,
and his research spans a wide range of topics within the field of chemistry. As a young professor, Ziegler
posed the question: what factors contribute to the dissociation of carbon-carbon bonds in substituted
ethane derivatives? This question was to lead Ziegler on to a study of free radicals, organometallics, ring
compounds, and, finally, polymerization processes.[4]

Free radical compounds

While still a doctoral student at
University of Marburg, Ziegler
published his first major article which
showed how halochromic (R3C+Z−)
salts could be made from carbinols.
Previous work had left the impression
that halochromic salts or free radicals Example of three tri-valent carbon free radicals. 1. 1,2,4,5-
(R3C•) required R to be aromatic. He tetraphenylallyl. 2. pentaphenylcyclopentadienyl. 3.
was encouraged to try to synthesize triphenylmethyl.
similarly substituted free radicals, and
successfully prepared 1,2,4,5-
tetraphenylallyl in 1923 and pentaphenylcyclopentadienyl in 1925. These two compounds were much
more stable than previous tri-valent carbon free radicals, such as triphenylmethyl. His interest in the
stability of tri-valent carbon free-radical compounds brought him to publish the first of many publications
in which he sought to identify the steric and electronic factors responsible for the dissociation of hexa-
substituted ethane derivatives.[13]

Many-membered ring compounds

Ziegler's work with many-membered ring compounds also utilized the reactive nature of alkali metal
compounds. He used strong bases such as the lithium and sodium salts of amines, to accomplish the
cyclization of long-chain hydrocarbons possessing terminal cyano groups. The initially formed ring
compound was then converted to the desired macrocyclic ketone product. Ziegler's synthetic method,
which included running reactions at high dilution to favor the intramolecular cyclization over competing
intermolecular reactions, resulted in yields superior to those of existing procedures (Laylin): he was able
to prepare large-ringed alicyclic ketones, C14 to C33, in yields of 60–80%.[4] An outstanding instance of
this synthesis was the preparation of muscone, the odiferous principle of animal musk by Leopold
Ružička.[11] Ziegler and co-workers published the first of their series of papers on the preparation of large
ring systems in 1933. For his work in this area and in free-radical chemistry he was awarded the Liebig
Memorial Medal in 1935.[13]

Organometallic compounds
Ziegler's work with free radicals led him to the organo compounds of the alkali metals. He discovered
that ether scission opened a new method of preparing sodium and potassium alkyls,[11] and found that
these compounds could easily be converted to the hexa-substituted ethane derivatives. The nature of the
substituent could be easily and systematically altered using this synthetic route by simply changing the
identity of the ether starting material.[13]

Lithium alkyls
Later, in 1930, he directly synthesized lithium alkyls and aryls from metallic lithium and halogenated
hydrocarbons via metal–halogen exchange. This convenient synthesis spurred numerous studies of RLi
reagents by others, and now organolithium reagents are one of the most versatile and valuable tools of the
synthetic organic chemist. Ziegler's own research on lithium alkyls and olefins was to lead directly to his
discovery of a new polymerization technique some 20 years later.

Living polymerization
In 1927, he found that when the olefin stilbene was added to an ethyl ether solution of phenylisopropyl
potassium, an abrupt color change from red to yellow took place. He had just observed the first addition
of an organoalkali metal compound across a carbon-carbon double bond. Further work showed that he
could successively add more and more of the olefinic hydrocarbon butadiene to a solution of
phenylisopropyl potassium and obtain a long-chain hydrocarbon with the reactive organopotassium end
still intact. Oligomers such as these were the forerunners of the so-called "living polymers".

Polyethylene
Since Ziegler was working at the Max Planck Institute for Coal Research, ethylene was readily available
as a byproduct from coal gas. Because of this cheap feedstock of ethylene and the relevance to the coal
industry, Ziegler began experimenting with ethylene, and made it a goal to synthesize polyethylene of
high molecular weight. His attempts were thwarted because a competing elimination reaction kept
occurring causing an anomalous result: instead of ethylene being converted into a mixture of higher
aluminum alkyls, its dimer, 1-butene, was almost the only product. It was reasoned that a contaminant
must have been present to cause this unexpected elimination reaction,[13] and the cause was eventually
determined to be traces of nickel salts. Ziegler realized the significance of this finding; if a nickel salt
could have such a dramatic influence on the course of an ethylene-aluminum alkyl reaction, then perhaps
another metal might delay the elimination reaction. Ziegler and his student H. Breil found that salts of
chromium, zirconium, and especially titanium did not promote the R2AlH-elimination but, instead,
enormously accelerated the "growth" reaction. Simply passing ethylene, at atmospheric pressure, into a
catalytic amount of TiCl3 and Et2AlCl dissolved in a higher alkane led to the prompt deposition of
polyethylene. Ziegler was able to obtain high molecular weight polyethylene (MW > 30,000) and, most
importantly, to do so at low ethylene pressures. The Ziegler group suddenly had a polymerization
procedure for ethylene superior to all existing processes.

Ziegler–Natta catalyst
In 1952, Ziegler disclosed his catalyst to the Montecatini Company in Italy, for which Giulio Natta was
acting as a consultant. Natta denoted this class of catalysts as "Ziegler catalysts" and became extremely
interested in their ability and potential to stereoregularly polymerize α-olefins such as propene.[13]
Ziegler, meanwhile concentrated mainly on the large-scale production of polyethylene and copolymers of
ethylene and propylene. Soon the scientific community was informed of his discovery. Highly crystalline
and stereoregular polymers that previously could not be prepared became synthetically feasible. For their
work on the controlled polymerization of hydrocarbons through the use of these novel organometallic
catalysts, Karl Ziegler and Giulio Natta shared the 1963 Nobel Prize in Chemistry.

Awards and honours

Karl Ziegler received many awards and honors. The following highlights
some of the most significant awards:

Liebig-Denkmünze medal (1935); This medal was awarded by

the present day German Chemical Society and is given to a
German chemist for their outstanding accomplishments and
creativity. Ziegler received the award because of his work in the
synthesis of multi-membered ring systems and stable tri-valent
carbon radicals.
War Merit Cross, 2nd class (19 October 1940)
Carl Duisberg Plakette (1953); This award is given for
outstanding service to the promotion of chemistry from the
German Chemical Society. Memorial tablet of the
GDCh.
Lavoisier Medal (1955); This award is given by the French
Chemical Society to scientists in various disciplines of
chemistry.
Carl Engler Medal (1958); This award is given by the German Society of Petroleum Science
and Coal Chemicals, of which he was the president in earlier years.
Werner von Siemens Ring (1960); This ring is awarded by the Werner von Siemens
Foundation and is considered the highest German award for individuals who by their
performance and skills opened up new technological paths.
Nobel Prize in Chemistry (1963); "[His] excellent work on organometallic compounds has
unexpectedly led to new polymerization reactions and thus paved the way for new and
highly useful industrial processes."[7]
Swinburne Medal of the Plastics Institute, London (1964); This award recognizes an
individual who has made a significant advancement to the science, engineering or
technology of plastics.
 Grand Merit Cross with Star and Sash (Großes Verdienstkreuz mit Stern und Schulterband)
of the Federal Republic of Germany (1964)
International Synthetic Rubber Medal of Rubber and Plastics Age (1967)
Grand Federal Cross of Merit (Order of Merit of the Federal Republic of Germany)(1969);
Ziegler was given this award for his work in the area of Science and Technology.
Pour le Mérite for Arts and Sciences (formerly Peace Class) (1969)
Foreign Member of the Royal Society (1971) [14]
Wilhelm Exner Medal (1971).[15]
Memorial tablet of the German Chemical Society under the Historic Landmarks of Chemistry
program (Historische Stätten der Chemie) at the Max Planck Institute for Coal Research in
Mülheim an der Ruhr (2008)
Honorary doctorates from the Technical University of Hannover, Giessen University,
University of Heidelberg and Darmstadt Technical University
The Karl-Ziegler-Schule in Mülheim was named after Ziegler
The Karl Ziegler Foundation is located at the German Chemical Society and gives the
Science Award, the Karl Ziegler Prize (worth 50,000 euros)

See also
Dienone–phenol rearrangement
List of Nobel laureates in Chemistry

References
1. Nobel Lectures, Chemistry 1963–1970. Amsterdam: Elsevier Publishing Company. 1972.
2. Bawn, C. E. H. (1975). "Karl Ziegler 26 November 1898 -- 11 August 1973" (https://doi.org/1
0.1098%2Frsbm.1975.0019). Biographical Memoirs of Fellows of the Royal Society. 21:
569–584. doi:10.1098/rsbm.1975.0019 (https://doi.org/10.1098%2Frsbm.1975.0019).
JSTOR 769696 (https://www.jstor.org/stable/769696).
3. Sherby, Louise (2002). The Who's Who of Nobel Prize Winners 1901–2000 (Fourth ed.).
Westport, CT: Oryx Press. ISBN 1-57356-414-1.
4. Eisch, John J. (1983). "Karl Ziegler: Master Advocate for the Unity of Pure and Applied
Research". Journal of Chemical Education. 60 (12): 1009–1014.
Bibcode:1983JChEd..60.1009E (https://ui.adsabs.harvard.edu/abs/1983JChEd..60.1009E).
doi:10.1021/ed060p1009 (https://doi.org/10.1021%2Fed060p1009).
5. Haenel, Matthias (8 May 2008). "Historical Sites of Chemistry: Karl Ziegler" (http://www.anal
yticjournal.de/ak_pat_historie/ziegler_gdch/ziegler_broschuere_gdch.pdf) (PDF). Booklet (in
German). Max-Planck-Institute for Coal Research. Retrieved 9 April 2010.
6. "Karl Ziegler" (http://www.britannica.com/EBchecked/topic/657091/Karl-Ziegler). Retrieved
9 April 2010.
7. Karl Ziegler (https://www.nobelprize.org/laureate/228) on Nobelprize.org , accessed 1 May
2020 including the Nobel Lecture on 12 December 1963 Consequences and Development
of an Invention
8. Guenther Wilke (2003). "Fifty Years of Ziegler Catalysts: Consequences and Development
of an Invention". Angewandte Chemie. 42 (41): 5000–5008. doi:10.1002/anie.200330056 (ht
tps://doi.org/10.1002%2Fanie.200330056). PMID 14595621 (https://pubmed.ncbi.nlm.nih.go
v/14595621).
 9. Ernst Klee: Das Personenlexikon zum Dritten Reich. Wer war was vor und nach 1945.
Fischer Taschenbuch Verlag, Second extended edition, Frankfurt am Main 2005, ISBN 978-
3-596-16048-8, p. 694 citing Henrik Eberle: Die Martin-Luther-Universität [Halle] in der Zeit
des Nationalsozialismus 1933–1945, Halle 2002.
10. Bernhard vom Brocke, Hubert Laitko (editors): Die Kaiser-Wilhelm-, Max-Planck-
Gesellschaft und ihre Institute. Das Harnack-Prinzip. de Gruyter, Berlin 1996, ISBN 3-11-
015483-8, S. 487f.
11. Oesper, Ralph E. (September 1948). "Karl Ziegler". Journal of Chemical Education. 25 (9):
510–511. Bibcode:1948JChEd..25..510O (https://ui.adsabs.harvard.edu/abs/1948JChEd..2
5..510O). doi:10.1021/ed025p510 (https://doi.org/10.1021%2Fed025p510).
12. "Karl Ziegler Schule" (http://www.karlzieglerschule.de) (in German). Retrieved 19 March
2010.
13. Bonnesen, Peter V. (1993). Laylin K. James (ed.). Nobel Laureates in Chemistry, 1901–
1992 (https://archive.org/details/isbn_9780841226906) (3 ed.). Washington, D.D.: Chemical
Heritage Foundation. pp. 449–455 (https://archive.org/details/isbn_9780841226906/page/44
9). ISBN 0-8412-2690-3.
14. "Library and Archive Catalogue" (http://www2.royalsociety.org/DServe/dserve.exe?dsqIni=D
serve.ini&dsqApp=Archive&dsqCmd=Show.tcl&dsqDb=Persons&dsqPos=0&dsqSearch=%2
8Surname%3D%27ziegler%27%29). Royal Society. Retrieved 2 November 2010.
15. Editor, ÖGV. (2015). Wilhelm Exner Medal. Austrian Trade Association. ÖGV. Austria.

External links
Karl Ziegler (https://www.nobelprize.org/laureate/228) on Nobelprize.org including the Nobel
Lecture, 12 December 1963 Consequences and Development of an Invention

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