The History of Polymer Science

THE HISTORY OF POLYMER SCIENCE 1.2.1. The Birth of Polymer Science 

It was the analysis of Hevea rubber that led to the acknowledgement of the existence of macromolecules where the monomer units are connected by covalent bonds. Samuel Shrowder Pickles of the Royal Institute of London was the first to propose a chain structure based on 

Lactuca sativa Fiscus elastica Helianthus annuus 

FIGURE 1.1. Examples of rubber-producing plants (Wikimedia Commons). 

FIGURE 1.2. Suggested building blocks of NR before (a) and after (b) 1910. 

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The discovery and development of polypropylene, the one genuinely new large tonnage thermoplastics material developed since World War II, forms part of what is arguably the most important episode in the history of polymer science. For many years it had been recognised that natural polymers were far more regular in their structure than synthetic polymers. Whilst there had been some improvement in controlling molecular architecture, the man-made materials, relative to the natural materials, were structurally crude. 

This publication is the record of the papers given and of the discussions at a meeting convened in May 1950 at Trinity College, Dublin by D.C. Pepper which is usually referred to as the First International Cationic (occasionally just Ionic) Symposium (A). It is important in the history of polymer science because many important new ideas were discussed there, some for the first time. These included Dainton and Ivin s theory of equilibrium polymerisations, co-catalysis (Plesch, Polanyi and Skinner), and the energetics of polymerisations. The present author made several contributions to that discussion, the most substantial of which was a joint theoretical paper which is reproduced here ... 

Professor Mark s story is told in three chapters by the Editor and four reminiscences by Rudolf Brill (whose association with Mark dates back to 1922), Hans Mark (his son), Linus Pauling, and Maurice Morton. The history of polymer science is given in separate chapters by the Editor, Robert Simha (who has worked with Professor Mark in two countries), and Carl Speed Marvel. One chapter by Charles Carraher gives an up to the minute report on the status of polymer education. The remainder of the book is a collection of reviews and previews of specific, timely topics in polymer science. Despite the diversity of topics, each area covered has contributions from Herman Mark. 

He has earned a lasting place in the history of polymer science through his research contributions, the successes of his students, his organizational genius, and his tireless promotion of the science and its students. It is entirely accurate to say that Herman Mark found polymers a curiosity and made them a science. 

Throughout the history of polymer science there have been efforts to improve (increase) the Tg to increase the useful operating temperature range of polymers. The preponderance of the literature has concentrated on mechanically blended polymeric systems with little component interaction on the molecular level. Where epoxy systems are concerned, the incorporation of additives into the systems results in many changes to the morphology and physical behavior of the material formed. 

Milestones in the history of polymer science (Morawetz, 1985, Percec, 2001, Hawker and Wooley, 2005)... 

The history of polymer science can be followed best with the books Morawetz H (1985) Polymers, The Origin and Growth of a Science. Wiley, New York and Furukawa Y (1998) Inventing Polymer Science Staudinger, Carothers, and the Emergence of Macromolecular... 

Government and University Research. In the history of polymer science, a major shift occurred, shared... 

Seymour, Raymond B., ed. Pioneers in Polymer Science Chemists and Chemistry. Boston Kluwer Academic Publishers, 1989. This survey of the history of polymer science emphasizes the scientists responsible for the innovations. Several of the chapters were written by scientists who were directly involved in these developments. 

R. B. Seymour, Ed., The History of Polymer Science and Technology (Marcel Dekker, New York, 1982). 

The history of polymer science (169,170), takes the reader back to before the macromolecular hypothesis. Natural rubber, civ-polyisoprene, was investigated around the turn of the twentieth century. Morawetz (169) writes of the destructive distillation of rubber to isoprene, and of the ozonolysis of rubber to levulinic aldehyde. These studies led to the dimer ring structure of dimethyl-cyclooctadiene for ds-polyisoprene ... 

A major milestone in the history of polymer science was the macromolecular hypothesis by Staudinger [1]. The molecular structure of polymers started to emerge and nowadays, almost 80 years later, a knowledge base of respectable size has been built by the contributions of thousands of researchers. Nevertheless, there are still many aspects of free-radical polymerizations that are not fully understood. The bimolecular free-radical termination reaction is one such example. The first scientific papers dealing in some detail with the kinetics of this reaction, can be traced back to the 40 s when the gel-effect was discovered [2-4]. From subsequent research it became apparent that this reaction has a very low activation energy and is diffusion controlled under almost all circumstances. A major consequence of this diffusion-controlled nature is that the termination rate coefficient kt) is governed by the mobility of macroradicals in solution and is thus dependent upon all parameters that can exert an effect on the mobility of these coils. Consequently, kt is a highly system-specific rate coefficient and benchmark values for this coefficient do not exist. 

In 1927 there appeared on the scene the most remarkable figure in the history of polymer science. Wallace Hume Carothers was born in rural Iowa in 1896. He was a high school prodigy. 

My serious interest in the history of polymer science was stimulated by Herbert Morawetz and his ground breaking monograph Polymers—The Origins and Growth of a Science. He has been a constant source of encouragement. 

A concluding essay discusses the prehistory and evaluates the various forces that influenced the history of polymer science. Actual human culture is driven by multiple factors and is both more complicated and more interesting than ideological stances. Polymer science provides a rich milieu in which to explore the development of a scientiflc community. 

John D. Ferry is known as the leading figure in the history of polymer science on the subject of viscoelasticity. He graduated from Stanford University at the age of 19, as noted above. For his doctoral work with George Parks he studied the properties of polyisobutylene as a function of temperature. He found the glass transition temperature and characterized the viscoelastic properties (Fig. 5.6). 

The period from 1935-1953 was a very profitable and dynamic era in the history of polymer science. The worldwide community that coalesced in 1935 was very active in identifying the key phenomena and forging satisfying qualitative and quantitative theories. The state of the commimity in 1953 will be surveyed from several perspectives. 

Because the development of polymerization catalysts and the processes for the commercial use are intimately associated with certain individuals, it will be of interest to mention these ingenious people in this chapter. More detailed accounts of the history of polymer science can be found in several interesting books [2-4]. 

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