Polymer Science Overview - ACS Publications - American Chemical

6 Herman F. Mark: The Geheimrat G. A L L A N STAHL

Downloaded by UNIV OF CALIFORNIA SAN DIEGO on January 21, 2016 | http://pubs.acs.org Publication Date: December 10, 1981 | doi: 10.1021/bk-1981-0175.ch006

Phillips Petroleum Company, Research and Development, Bartlesville, OK 74004

"Once in Ludwigschafen the laboratory director, O. Seidl, told me, 'Mark, you should go into business. If you are as successful in making money as you were in spending it on research we can already congratulate ourselves.'" H.F. Mark

The years Mark worked in Berlin in retrospect set the stage for his rocket like rise to eminence in polymer science. Postwar inflation placed many of Berlin's bolder attractions out of the reach of the young scientist and his new bride, Mimi. In place of the expensive frolics, the Mark's entertained and exchanged ideas with an international set of coworkers in his Lichterfelde-West apartment. Besides his fellow Austrians, Mark's close friends included Hungarians and Poles, as well as Germans. This broad mesh of backgrounds and styles of thinking was catalyzed by the unexcelled and readily available music, art, and architecture, and stimulated by such scientists as Schroedinger, Haber, Hahn, V. Laue, Einstein, Planck, Nerst, and Schlenk. The result was it expanded his perspective, taught him how to communicate and lead a diverse group of scientists despite problems of differing nationality and proclivity, and enhanced his natural sagacity as only a broad range of experiences can. A broadening i n Mark's i n t e l l e c t i s shown c l e a r l y i n h i s publications of t h i s period. The t o p i c s i n 1926 and 1927 alone ranged from atomic s t r u c t u r e and quantum theory (1) , and Compton r a d i a t i o n (2) to the s c a t t e r i n g o f x-rays by an i d e a l gas Ç3) and m i n e r a l s t r u c t u r e (4). The shear d i v e r s i t y of h i s contacts and i n t e r e s t s made him q u a l i f i e d f o r expanded responsibilities.

0097-6156/81/0175-0061$6.75/0 © 1981 American Chemical Society

In Polymer Science Overview; Stahl, G. Allan; ACS Symposium Series; American Chemical Society: Washington, DC, 1981.

62

POLYMER SCIENCE OVERVIEW

P r o f e s s o r F r i t z Haber, D i r e c t o r of the K a i s e r Wilhelm I n s t i t u t e , no doubt had t h i s i n mind when he c a l l e d Mark to h i s v i l l a during the summer of 1926. In a v i s i t reminscent of Haber and S c h l e n k s meeting which brought Mark to the I n s t i t u t e a few years before, Haber o u t l i n e d Mark's achievements and described a new opportunity f o r advancement, t h i s time i n the chemical industry. The p o s i t i o n was as an A s s i s t a n t D i r e c t o r of Research under Kurt H. Meyer with the g i a n t I.G. Farbenindustrie. Research at I.G. Farben at that time was conducted i n f i v e l a r g e r e s e a r c h l a b o r a t o r i e s . I n o r g a n i c chemistry was the primary research area at B i t t e r f e l d under L. P i s t o r , w h i l e pigments and pharmaceuticals were studied at Leverkusen under C. Duisberg and at Hoechst under E. Schmidt. Research of ammoniacal f e r t i l i zers was conducted at Oppau under A. M i t t a s c h . The f i f t h l a b o r a t o r y was the c e n t r a l l a b o r a t o r y i n Ludwigschafen, headed by Meyer. Meyer, who was a l s o an executive of the company, sought an e n e r g e t i c , d i v e r s e i n d i v i d u a l to d i r e c t the l a b o r a t o r y i n a concentrated study of f i b e r s and f i l m s . In the p e r i o d ensuing the F i r s t World War, the I . G. f a c t o r i e s had switched from guncotton manufacture to c e l l u l o s e acetate and v i s c o s e , but too l i t t l e was known of the b a s i c c h a r a c t e r i s t i c s of these m a t e r i a l s to make s u b s t a n t i a l improvements on t h e i r p r o p e r t i e s . Further, i t was b e l i e v e d that s y n t h e t i c f i b e r s were p o s s i b l e , but t h e i r p r e p a r a t i o n was not p r a c t i c a l at that time. The f a r s i g h t e d Meyer recognized the business p o t e n t i a l that an understanding of the b a s i c nature of f i b e r - f o r m i n g substances could tap. When he interviewed w i t h Meyer i n 1926, Mark o u t l i n e d a t y p i c a l l y thorough program. He proposed a team of organic and p h y s i c a l chemists, and p h y s i c i s t s who would evaluate the i n f l u e n c e of s t r u c t u r e on p r o p e r t i e s such as r i g i d i t y , e l a s t i c i t y , m e l t i n g p o i n t , and water a b s o r p t i o n . Work, he proposed, would s h i f t toward new m a t e r i a l development and i n t o the manufacturing f a c i l i t i e s to evaluate the e f f e c t s of processing


T

on s t r u c t u r e as t h e i r knowledge base expanded. " A l l of t h i s , " Mark t o l d Meyer, "can be accomplished i f I have the necessary apparatus, equipment, and a few able p h y s i c i s t s , p h y s i c a l chemists, and, of course, a good organic chemist." Meyer approved and h i r e d Mark. In doing so he began simultaneously a very c l o s e , l i f e - l o n g f r i e n d s h i p and a prof e s s i o n a l r e l a t i o n s h i p which would help b r i n g I . G. Farben and polymer science to new heights. Mark moved from B e r l i n to Mannheim on January 1, 1927. In assuming h i s d u t i e s , Mark began an i n t e n s i v e period of p l a n t v i s i t s , l a b o r a t o r y design, and personnel h i r i n g . Six months afterward, he had h i r e d a number of e x c e l l e n t l y t r a i n e d s c i e n t i s t s such as p h y s i c i s t s J . Hengstenberg from F r e i b u r g , and R. W i e r l and K. Wolf from Munich. In a d d i t i o n , he brought p h y s i c a l chemists H. Dohse, G. V. Susich, E. Valko, H. K a l b e r e r ,


6.

STAHL

The Geheimrat

63


M. Dunkel and H. F i k e n t s c h e r , and, of course, "a good organic chemist" (or two) C. Wulff and H. Hopff. The group e v e n t u a l l y numbered about f i f t y with f i f t e e n s c i e n t i s t s , and were organized i n three s e c t i o n s — s y n t h e s i s , c h a r a c t e r i z a t i o n , and a p p l i c a t i o n s — w i t h Mark as the c o o r d i n a t o r . In a d d i t i o n by mid-1927, the I. G. could boast of the best X-ray d i f f r a c t i o n equipment on the c o n t i n e n t . Mark's i n c l i n a t i o n based on h i s r e s e a r c h at the F i b e r Research I n s t i t u t e was that " c o l l o i d a l " substances such as c e l l u l o s e and rubber were of high molecular weight. Work began with t h i s cornerstone concept. In the beginning r e s e a r c h was mostly concerned with t e s t i n g v i s c o s e and c e l l u l o s e a c e t a t e fibers. Before long a great d e a l of research was conducted on m a t e r i a l s subsequently c a l l e d a d d i t i o n polymers. The s y n t h e s i s s e c t i o n s y s t e m a t i c a l l y prepared new monomers, polymers, and an ever i n c r e a s i n g number of copolymers. At the same time, the c h a r a c t e r i z a t i o n and a p p l i c a t i o n s s e c t i o n s t e s t e d the polymers i n order to a s c e r t a i n which were worthy of l a r g e r s c a l e experiments, scale-up, and patent prot e c t i o n . They a l s o performed the work r e q u i r e d to s a t i s f y production d e t a i l s . These e f f o r t s , d i r e c t e d by Mark's p e r s o n a l hands-on s t y l e of management, were the f i r s t s e r i o u s attempts at commercialization of p o l y s t y r e n e , p o l y ( v i n y l c h l o r i d e ) , poly(methyl m e t h a c r y l a t e ) , and s y n t h e t i c rubber. Work with these m a t e r i a l s would have been l e s s p r o d u c t i v e had Mark have not simultaneously expanded the o r i g i n a l s t u d i e s to i n c l u d e a l a r g e number of r e l a t e d and seemingly u n r e l a t e d n a t u r a l substances. An incomplete, c h r o n o l o g i c a l review of Mark's p u b l i c a t i o n s of 1928 b r i n g s to l i g h t the methodical thoroughness of t h e i r r e s e a r c h . E a r l y i n the year, Mark published two fundamental papers d e a l i n g with the foundations of c r y s t a l s t r u c t u r e a n a l y s i s (_5) and Naegeli's m i c e l l u l a r concept (6). S h o r t l y afterward Hengstenberg and Mark (7), and Meyer and Mark (8) expanded the e x i s t i n g views and proposed c r y s t a l l i t e s of c e l l u l o s e and rubber, and s i l k r e s p e c t i v e l y . The proposed c r y s t a l l i t e s were much l a r g e r than the commonly accepted ( c o l l o i d - ) a s s o c i a t i o n theory would permit. T h i s a s s e r t i v e n e s s was simultaneously supportive of Staudinger's high molecular weight concept or macromolecules, and i n s t r u c t i v e regarding the p r o p e r t i e s of r e l a t e d n a t u r a l and s y n t h e t i c m a t e r i a l s . In t h i s same year, Mark published papers on c h i t i n (9), rubber (10), and s t a r t e d an exhaustive study of the s t r u c t u r e of c e l l u l o s e . I t i s i n t e r e s t i n g to note that i n t h e i r f i r s t paper on c e l l u l o s e (11) Meyer and Mark proposed a s t r u c t u r a l u n i t c e l l model which i s c l a s s i c and accepted, f o r the l a r g e s t p a r t , even today. They proposed a c e l l u l o s e c r y s t a l l i t e i n which a l l


64



atoms were bound to each other i n very long chains by primary valence f o r c e s , and the chains i n turn aggregated i n l a r g e r combinations by secondary f o r c e s . The s i m p l i c i t y of t h i s concept i s misleading. I t represented a compromise between the a s s o c i a t i o n theory of molecular i n t e r a c t i o n and macromol e c u l e s , while a c t u a l l y embracing the l a t t e r . In the f o l l o w i n g years, Mark published s i x other papers on c e l l u l o s e , s t a r c h , and sugar. Meyer and Mark's c o n t r i b u t i o n s to the development of a polymer theory and r e l a t i o n s h i p w i t h P r o f e s s o r Hermann Staudinger are the subject of a subsequent s e c t i o n . Mark's c o n t r i b u t i o n s w h i l e at the I . G. were not l i m i t e d to the emerging f i e l d of polymer s c i e n c e . In those f i v e years, he a l s o took part i n s t u d i e s of X-ray o p t i c s and continued h i s study of the X-ray s t r u c t u r e of metals and metal s a l t s . Other seemingly unrelated paper were published on the width of X-ray emission l i n e s (12), Schlenk isomerism (13), the s t r u c t u r e of aromatic compounds (14), and a s p e c i a l "hobby" the o p t i c a l Stark E f f e c t (15, 16). Regarding t h i s l a t t e r work, Mark r e l a t e s that h i s s u p e r v i s o r s t o l e r a t e d the research commenting that "as long as they are doing something decent and important" i t was okay "as sport doesn't cost much money". In 1930, R. W i e r l and Mark studied N. Davidson and J . Germer's experiments on e l e c t r o n d i f f r a c t i o n . Employing t h e i r wide experience i n instrumentation, they promptly cons t r u c t e d an improved e l e c t r o n s c a t t e r i n g apparatus. With t h i s instrument, they determined the interatomic d i s t a n c e s i n a number of molecules and published a s e r i e s of papers on the technique and t h e i r f i n d i n g s (17, 18, 19). Mark's c o n t r i b u t i o n s to the f i e l d of c r y s t a l s t r u c t u r e are discussed i n a l a t e r chapter of t h i s volume and w i l l not be covered i n more d e t a i l here (see P a u l i n g , L. "Herman Mark and the S t r u c t u r e of C r y s t a l s " , t h i s volume.). Throughout the Ludwigschafen years Mark and h i s a s s o c i a t e s maintained c l o s e contact w i t h the U n i v e r s i t i e s at Heidelberg and F r e i b e r g and technische hochschulen at Darmstadt and K a r l sruhe. In Heidelberg they consulted w i t h K a r l Freudenberg, who was w e l l known f o r h i s fundamental c o n t r i b u t i o n s toward the acceptance of the chain s t r u c t u r e of c e l l u l o s e . As we s h a l l d i s c u s s l a t e r , they c o l l o b o r a t e d w i t h Hermann Staudinger at Freiberg. Staudinger, i n a d d i t i o n to h i s organic chemical preparations, ketene s t u d i e s , and ground breaking work i n macromolecules, a l s o produced a l a r g e number of h i g h l y q u a l i f i e d a s s i s t a n t s , s e v e r a l of whom l a t e r worked f o r I. G. Farben. Close contact was maintained with the schools at Darmstadt where E. B e r l was a c t i v e l y i n v o l v e d i n the e v a l u a t i o n of the t e c h n i c a l p r o p e r t i e s of c e l l u l o s e and i t s d e r i v a t i v e s , and Karlsruhe. Mark was an a s s o c i a t e professor at Karlsruhe, and a c c o r d i n g l y observed G. Bredig and A. R e i s ' s t u d i e s of the p h y s i c a l chemistry of c o l l o i d s and c r y s t a l s .



6.

STAHL

The Geheimrat

Figure 1.

I. G. Farben scientists with Professor J. R. Katz (seated) in Ludwigschafen in 1929; Dr. H. F. Mark is standing at the far right.


65


66

POLYMER SCIENCE

OVERVIEW

The i n d e f a t i g a b l e Mark c o u l d i n these years be found at work at n e a r l y any hour. From h i s morning shave f r e q u e n t l y taken i n h i s o f f i c e to a l a t e evening conference i n a l o c a l wine c e l l a r , Mark l e c t u r e d , wrote, coaxed, pushed, defended, and shoved h i s r e s e a r c h e r s to seldom matched l e v e l s of production. One coworker at Ludwigschafen r e c e n t l y commented, h i s "astounding amount of work, e s p e c i a l l y h i s c o n t r i b u t i o n s i n books and papers was unthinkable without economy of work and many hours of overtime" (20). The same can be s a i d f o r the whole l a b o r a t o r y . Through t h e i r e f f o r t s , I . G. Farben was the world l e a d i n g c o r p o r a t i o n i n commercializing new polymers and copolymers. A l i s t of t h e i r polymers which were commercialized i n the e r a i n c l u d e s p o l y s t y r e n e , p o l y ( v i n y l c h l o r i d e ) , poly(methyl methacryl a t e ) , p o l y ( v i n y l a l c o h o l ) , and the f i r s t s y n t h e t i c rubbers, Buna-N and Buna-S. Among many other accomplishments, the l a b o r a t o r y was a leader i n knowledge of polymer s t r u c t u r e as w e l l as c o p o l y m e r i z a t i o n , f i r s t ( a f t e r a Mark v i s i t to the F r a n k f u r t Arboretum) i n developing peroxide p o l y m e r i z a t i o n i n i t i a t o r s , at the f o r e f r o n t i n the development of new equipment ranging from X-ray and e l e c t r o n d i f f r a c t i o n apparatus to f i b e r spinning n o z z e l s , and one of the f i n e s t X-ray a n a l y s i s l a b o r a t o r i e s anywhere. Mark's p e r s o n a l r e c o r d between 1927 and 1932, h i s years w i t h I . G. Farben, i n d i c a t e s over e i g h t y p u b l i c a t i o n s , seventeen patents (issued to I . G. Farben), and three books. Two coauthored by Meyer and Mark, "Aufbau der Hochpolymeren Substanzen" (21) and "Der Aufbau der Hochpolymeren Organischen N a t u r s t o f f " (22), were p r i n t e d s e v e r a l times, and were considered t e x t s of the day. "Die Experimentellen und Theoretischem Grundlagen der Elektronenbeugung" (23) was w e l l accepted. Mark a l s o p u b l i s h e d a t r e a t i s e on the "Physik und Chemie der C e l l u l o s e " (24) during t h i s p e r i o d . The charmed times ended during the summer of 1932. The p o l i t i c a l s i t u a t i o n i n Germany swung and favored an imminent assumption of power by the N a t i o n a l S o c i a l i s t s P a r t y . Mark's p o s i t i o n , although p e r s o n a l l y a p o l i t i c a l , was p r e c a r i o u s because of h i s Jewish h e r i t a g e . A d i r e c t o r of the Ludwigschafen and Oppau works, F. Gaus, advised him to look f o r an academic position. Gaus f u r t h e r agreed to support Mark i n an academic p o s i t i o n f o r three years a f t e r l e a v i n g the I.G. to ease discomfort during the p e r i o d of establishment. Mark accepted t h i s generous, a l t r u i s t i c o f f e r , and a f t e r c o n s i d e r i n g s e v e r a l a t t r a c t i v e o f f e r s , a l l u n f o r t u n a t e l y i n Germany, he accepted a p o s i t i o n at the U n i v e r s i t y of Vienna. In October, 1932, Mark, h i s w i f e , and two sons moved to Vienna. About the same time h i s c l o s e f r i e n d , c o l l a b o r a t o r , and former s u p e r v i s o r , Κ. H. Meyer, moved to Geneva.


6.

STAHL

The Geheimrat

67


"Because of small d i f f e r e n c e s i n neighboring opinions, a l a r g e r point of view o f t e n does not get enough a t t e n t i o n . " H. F. Mark

"Mark w i l l NEVER have a p r i o r i t y f i g h t . He i s only unhappy i f a person allows something to d i e on the v i n e . " E. Proskauer

When Herman Mark f i r s t evaluated the c r y s t a l s t r u c t u r e of rubber (with E. A. Hauser) and c e l l u l o s e (with J . R. Katz) i n 1924 and 1925, i t was g e n e r a l l y accepted that these m a t e r i a l s were low molecular weight or monomeric. The unusual p r o p e r t i e s of these substances, now known to be r e l a t e d to high molecular weight, were then a t t r i b u t e d to aggolomeration or " a s s o c i a t i o n " of the low molecular weight p r e c u r s o r s . A common e x p l a n a t i o n f o r the a s s o c i a t i o n s were secondary f o r c e s such as Johannes Thiele's p a r t i a l valences. T h i s concept, the a s s o c i a t i o n theory, was not l a c k i n g i n e i t h e r supporters or b a s i s . I t grew from the c o l l o i d theory of Thomas Graham, was r e i n f o r c e d by T h i e l e , and took i t s u l t i m a t e expression from three important s c i e n t i f i c developments of the e a r l y twentieth century. They were, according to Olby (25), the i n t r o d u c t i o n of A. Werner's concept of two kinds of combining f o r c e s — p r i m a r y and secondary v a l e n c e s , the extension of c o l l o i d s c i e n c e i n t o b i o l o g y (thus g a i n i n g i t r e p u t a b l e r e c o g n i t i o n ) , and the seeming support of the low molecular weight concept by X-ray crys t a l l o g r a p h y . T h i s l a t t e r support was based on the then accepted idea that the molecule could not be l a r g e r than the u n i t c e l l of the c r y stal. In a d d i t i o n , supporters noted that the c o l l o i d a l p r o p e r t i e s of many substances such as soaps are based on the c r e a t i o n of l a r g e aggregates of small s i n g l e molecules. f

There was, t h e r e f o r e , good reason i n the 1920 s to assume an analogous foundation f o r rubber, c e l l u l o s e , and other r e l a t e d m a t e r i a l s . Not everyone agreed. Workers i n p r e p a r i n g "rubber l i k e " substances from isoprene had, s i n c e the turn of the century, been e x p l a i n i n g the r e s u l t a n t p r o p e r t i e s by use of ever expanding combined isoprene r i n g s . C. H a r r i e s and S. S. P i c k l e s were independently p r e d i c t i n g up to seven and eight isoprene u n i t s i n rubber, but the point of view was l e s s commonly accepted than the a s s o c i a t i o n theory. The death k n e l l f o r the a s s o c i a t i o n theory began i n 1920. That year H. Staudinger published an important paper c a l l e d "Uber P o l y m e r i s a t i o n " (26). The paper was a summary of h i s f i n d i n g s over s e v e r a l years r e g a r d i n g high molecular weight. The concepts put f o r t h i n that paper, the proposed l i n e a r chain


68

POLYMER SCIENCE

OVERVIEW


formulas f o r p o l y s t y r e n e and polyoxymethylene f o r example, are s t i l l v a l i d today. As a r e s u l t of h i s many c o n t r i b u t i o n s to the development of polymer or (as he c a l l e d i t ) macromolecular theory, Staudinger was awarded the Nobel P r i z e i n Chemistry i n 1953. Acceptance of Staudinger's ideas d i d not come q u i c k l y , and Mark and h i s a s s o c i a t e , Κ. H. Meyer, played important r o l e s . T h e i r c o n t r i b u t i o n s and r e l a t i o n s h i p with Staudinger i s an i n t e r e s t i n g b i t of s c i e n t i f i c h i s t o r y (27). In 1926 Staudinger was t o t a l l y involved i n defending h i s ideas r e g a r d i n g the macromolecule. On the other hand, Mark, at the F i b e r Research I n s t i t u t e i n Dahlem, was r i d i n g the c r e s t of a c c l a i m as an outstanding c r y s t a l l o g r a p h e r and expert i n molecular s t r u c t u r e . The two were requested to present papers by R. W i l l s t a e t t e r at a s p e c i a l symposium of the " G e s e l l s c h a f t Deutscher N a t u r f o r s c h e r und A r z t e " . The symposium was held on September 23, 1926, i n Dusseldorf. I t was a c l a s s i c showdown between a s s o c i a t i o n theory c o n s t i t u e n t s , M. Bergmann and H. Pringsheim supported by E. Waldschmidt-Leitz, and Staudinger. Mark was i n v i t e d by Chairman W i l l s t a e t t e r at the prompting of h i s c l o s e f r i e n d F. Haber to address the problem of molecular weight and elementary crystal c e l l size. Q u a n t i f i c a t i o n , as W i l l s t a e t t e r , Haber, and Mark recognized, i n d i c a t e d no more than four r e s i d u e s i n the u n i t c e l l of c e l l u l o s e and s i l k . I f i n f a c t the molecule could be no l a r g e r than i t s elementary c e l l , t h i s was weighty evidence against the e x i s t e n c e of very l a r g e molecules. (Texts of the Bergman, Mark, Waldschmidt-Leitz, Pringsheim, and Staudinger p r e s e n t a t i o n s were p u b l i s h e d . The i n t e r e s t e d reader should consult: Ber., 1929, 59, 2973, 2982, 3000, 3008, 3019..) Bergmann opened the meeting and brought f o r t h the argument that the c l a s s i c theory of Kekule' chains was i n a p p r o p r i a t e to e x p l a i n the macroproperties of i n u l i n and i n general p r o t e i n s . As an example he r e f e r r e d to "psuedo-high molecular weight" i n o r g a n i c complexes. In a s i m i l a r f a s h i o n , Pringsheim d i s c u s s e d the nature of i n u l i n and other p o l y s a c c h a r i d e s . Bergmann and Pringsheim c i t e d the work of P. K a r r e r , K. Hess, and R. Pummerer and r e f e r r e d to primary and secondary bonding as proposed by Werner. Staudinger countered with a voluminous review of h i s work on rubber and s y n t h e t i c polymers. He supported h i s contentions of high molecular weight with s o l u t i o n v i s c o s i t y data and r e s u l t s of hydrogénation experiments on rubber, p o l y s t y r e n e and p o l y i n dene. The hydrogénation experiments were designed to demonstrate r e t e n t i o n of p r o p e r t i e s d e s p i t e l o s s of " a s s o c i a b l e " u n s a t u r a t i o n . His i n t e r p r e t a t i o n s were not widely accepted because of the elementary c e l l - molecular weight ambiguity. I t was a n t i c i p a t i o n of t h i s stalemate which prompted Mark's i n v i t a t i o n . Mark's paper, t i t l e d "Die roentgenographishe E r m i t t l u n g der Struktur organischer besonders hochmolekularer Substanzen", s y s t e m a t i c a l l y compared the a n a l y s i s of hexamethylenetetramine


The Geheimrat


STAHL

Figure 2.

Professor Hermann Staudinger at Freiberg im Breisgan on July 14, 1953.



70

POLYMER

SCIENCE OVERVIEW

with c e l l u l o s e . In a lengthy p r e s e n t a t i o n , he concluded that c e l l u l o s e i s h e l d together by f o r c e s "comparable i n type and magnitude to the inner molecular f o r c e s " and "the whole c r y s t a l l i t e appears as a l a r g e molecule". Reaction to the symposium was v a r i e d . A number of persons ( i n c l u d i n g Chairman W i l l s t a e t t e r ) were swayed i n favor of l a r g e molecules, while others were i n c r e d u l o u s . One r e s u l t of the meeting was extremely important. A f t e r Mark's p r e s e n t a t i o n the problem of r e l a t i n g the small elementary c e l l to high molecular weight was no longer an o b s t a c l e . S h o r t l y a f t e r the Dusseldorf meeting, Mark and Staudinger s t a r t e d exchanging l e t t e r s . On January 5, 1927, only a few days a f t e r s t a r t i n g h i s new p o s i t i o n at the I . G. Farben Ludwigschafen l a b o r a t o r y , Mark wrote and asked Staudinger f o r samples of polyoxymethylene decomposition products f o r new X-ray i n v e s t i g a t i o n s . Staudinger d e c l i n e d on the grounds that he was already i n v o l v e d i n s i m i l a r research with Hengstenberg (who j o i n e d Mark i n Ludwigschafen the f o l l o w i n g year) and Mie. The Mark-Staudinger r e l a t i o n s h i p was e x c e l l e n t and t h e i r contact by l e t t e r s and c o n s u l t a t i o n steady. In 1928, Κ. H. Meyer and Mark published an extensive paper on. the c r y s t a l s t r u c t u r e of c e l l u l o s e (11). They proposed a s t r u c t u r e which i s n e a r l y the same as that accepted today. According to t h e i r concept "part of the c e l l u l o s e i s amorphorus but can be chemically degraded; t h e r e f o r e , we do not doubt that the amorphorus part c o n s i s t s of long chains. We even consider i t probable that at the s u r f a c e of the c r y s t a l l i t e , the chains get g r a d u a l l y d i s o r d e r e d and form an amorphorus bark. We cannot say that the l e n g t h of the chain i s a c t u a l l y determined by X-ray diagrams. They can be much longer and g r a d u a l l y degenerate i n t o the bark." They a t t r i b u t e d the s t r e n g t h of c e l l u l o s e f i b e r s to covalent bonding of the molecules, and " i n s o l u b i l i t y and t e n a c i t y to the whole s t r u c t u r e , only when the main-valency chains themselves are of s u f f i c e n t l e n g t h " . T h e i r model i s a compromise between the a s s o c i a t i o n theory and Staudinger s macromolecules. ?

Staudinger disagreed with Meyer and Mark only on two p o i n t s . He b e l i e v e d t h e i r estimate of the main chains was too short and denied the existence of m i c e l l e s . These d i f f e r e n c e s were s l i g h t , and as P r i e s n e r r e p o r t s (27), there was i n t e r e s t on both s i d e s f o r an extensive exchange of ideas. While d i f f e r i n g on these p o i n t s , both concepts were s u b s t a n t i a l l y d i f f e r e n t from those of the a s s o c i a t i o n theory advocates. Then, a few months afterward Meyer repeated and g e n e r a l i z e d the c e l l u l o s e s t r u c t u r e to i n c l u d e c r y s t a l l i n e knots at r e g u l a r i n t e r v a l s (28). T h i s model was u s e f u l i n e x p l a i n i n g not only the p r o p e r t i e s of c e l l u l o s e , but those of rubber as w e l l . Staudinger c a l l e d the concept unusable, i n c o r r e c t , and dubbed i t "the New M i c e l l e Theory".


6.

STAHL

The

71

Geheimrat

S h o r t l y afterward, Staudinger f o r m a l l y c r i t i c i z e d Meyer and Mark's work. I t appears that i t was the second p u b l i c a t i o n which brought out Staudinger's o b j e c t i o n s . In a l e t t e r to Mark w r i t t e n October 31, 1928, Staudinger wrote: . . . finally, I a l s o have w r i t t e n a few papers opposing the views of Κ. H. Meyer. I do not agree w i t h him on two p o i n t s . F i r s t , i n my o p i n i o n , the statements of Κ. H. Meyer do not represent anything new, but rather c o i n c i d e i n general w i t h the opinions I have advocated f o r years and e s t a b l i s h e d experimentally. Second, I do not b e l i e v e that the i n t r o d u c t i o n of 'primary valence chains', i n s t e a d of macromolecules, solves any problem." Staudinger also s t a t e d these views p u b l i c l y (29). In h i s review of these events, P r i e s n e r (27) (the only published s c h o l a r of Staudinger's l e t t e r s ) r e p o r t s that of the supporters of the high molecular weight concept only Meyer and Mark were reproached f o r t h e i r views. Yet the "New M i c e l l e Theory" represented an independent p e r c e p t i o n of the i d e a s . F u r t h e r , P r i e s n e r a s s e r t s that Staudinger's o b j e c t i o n s regarding the "primary valence c h a i n s " must be evaluated i n the language of the time. He says that Staudinger's d e s i g n a t i o n f o r what we now c a l l polymers—macromolecule—was a t best on the b o r d e r l i n e of a c c e p t a b i l i t y . At that time, i t s d e f i n i t i o n i n f e r r e d that a l l the molecules were e x a c t l y a l i k e . Since the chains of a polymer, rubber f o r example, are s t r u c t u r e d the same and may not exceed c e r t a i n lengths, but are not e x a c t l y the same number of monomer u n i t s , the d e f i n i t i o n d i d not f i t . "Primary valence c h a i n " sidestepped t h i s problem. None-the-less the problem was of wording, f o r Staudinger, Meyer, and Mark understood that the polymers were p o l y d i s p e r s e . I n d i c a t i v e of t h i s , Staudinger wrote i n h i s reproach (29) that " i n the high polymers we do not have m a t e r i a l s with molecules having the same molecular s i z e , but mixtures of d i f f e r e n t lengths . . . One cannot speak of molecular weight but only of average molecular weight". Mark responded to Staudinger on November 2, 1928. Among other things he wrote, "I am s o r r y to see from your l e t t e r that you f e e l annoyed by the statements of P r o f e s s o r Meyer. I am convinced that i t was the l a s t t h i n g P r o f e s s o r Meyer intended to do. I have, i n our j o i n t research and e s p e c i a l l y i n my Hamburg l e c t u r e , emphasized the importance of your b e a u t i f u l work. I n t r o d u c t i o n of the term, primary valence chain, i s very purpose f u l s i n c e i t r e f e r s to s t r u c t u r e s which are not i d e n t i c a l . . . r a t h e r average lengths. I f we add t h i s f a c t to your macromole c u l e s , then both concepts become i d e n t i c a l . "Because of t h i s I p r e f e r not to emphasize the d i f f e r e n c e s . . . we mean the same t h i n g . I b e l i e v e that we should advocate t h i s point of view together and not emphasize some s l i g h t differences i n perceptions. The high polymer camp could e a s i l y make the mistake very w e l l known i n p o l i t i c s : because of small d i f f e r e n c e s i n neighboring o p i n i o n s , a l a r g e p o i n t of view o f t e n does not get enough a t t e n t i o n . "


11




Figure 3.

Professor Kurt H. Meyer in Geneva on July 19, 1951.



6.

STAHL

The

Geheimrat

73

Meyer (30) d i d not b e l i e v e that he could leave Staudinger's statements unanswered. He r e s t a t e d t h e i r agreement regarding the e x i s t e n c e of long molecular chains; however, objected to Staudinger p r e s e n t i n g h i s (Meyer's) opinions as h i s own. Meyer added that he had r e f e r r e d to Staudinger's work as o f t e n as necessary. Staudinger countered by p u b l i s h i n g a "Schlusswort" or f i n a l word (31), a copy of which he submitted to Meyer before p u b l i c a tion. In t h i s "Schlusswort" he reemphasized h i s p o s i t i o n and answered Mark's request f o r cooperation. I t i s i n t e r e s t i n g that Mark wrote an extensive l e t t e r to Staudinger a s k i n g him t o omit t h i s l a t t e r p a r t , s i n c e otherwise he too would have to respond, Staudinger's r e p l y to Mark i s not known, but the published "Schlusswort" i n d i c a t e s h i s compliance w i t h Mark's request. The debate might have ended here had Naturwissenschaften not have published a condensation of Meyer's Z e i t s c h r i f t f u e r Angewandte Chemie paper (28). Staudinger, then wrote i n the former p u b l i c a t i o n (32), "An a r t i c l e by Κ. H. Meyer . . . i s a condensation of a previous a r t i c l e . The opinions i n these p u b l i c a t i o n s about the s t r u c t u r e of high molecular weight compounds a r e presented i n a manner I have advocated f o r years i n many p u b l i c a t i o n s and speeches. I welcome that the author shares the opinions . . . s i n c e no r e f e r e n c e was made to my work, I have to assume t h a t Κ. H. Meyer b e l i e v e s t h i s i s common knowledge." In t h i s paper Staudinger objected t o the use of "primary valence c h a i n s " and m i c e l l e s . However, he d i d not exclude the p o s s i b i l i t y o f molecular a s s o c i a t i o n s . Although he denied the p o s s i b i l i t y of m i c e l l e s , he discussed c r y s t a l l i t e s . The c r y s t a l l i t e s and the m i c e l l e s o f Meyer and Mark were identical. Even though Mark's s t u d i e s of high molecular weight sub stances expanded during t h i s time, h i s p a r t i c i p a t i o n i n the polemics regarding h i s (and Meyer's) and Staudinger's opinions ceased. In the ensuing years Mark has repeatedly maintained that he shared the opinions of Meyer. F u r t h e r , he says that Meyer encouraged him to p a r t i c i p a t e . But f o r Mark, these were times of new s t u d i e s and new commercial developments. At no other time has Mark's b a s i c temperment shown more c l e a r l y . He d e s i r e d only to move forward, not to rehash past developments. A h a l f century l a t e r Mark s a i d two developments prevented h i s "more a c t i v e " involvement. One was h i s and Meyer's b e l i e f that Staudinger had completely e s t a b l i s h e d h i s p r i o r i t y i n proposing l o n g c h a i n s . The second was the work of W. H. Carother's which convinced him i n 1929 that the long c h a i n connection of n a t u r a l and s y n t h e t i c polymers would soon be irrevocably resolved.


74

POLYMER SCIENCE

OVERVIEW

"One day i n Ludwigschafen, the great s c i e n t i s t M i t t a s c h asked me, 'What are you d o i n g ? I s a i d I was measuring v i s c o s i t y . 'Why?' he asked. I t o l d him that we d e s i r e d to d e t e r mine the molecular weight of a polymer. About a h a l f year l a t e r I saw him at a con ference. He asked me, 'Say P r o f e s s o r , are you s t i l l working with those h i g h l y contaminated solutions?'" H. F. Mark


1

Herman Mark and (independently) Herman Staudinger were the f i r s t to suggest the v i s c o s i t y of a polymer s o l u t i o n was r e l a t e d to the molecular weight of the polymeric s o l u t e . In doing so, they were again going heads-on a g a i n s t the b e l i e f s of the a s s o c i a t i o n theory advocates. For according to the l a t t e r group's s t u d i e s , based f o r the greater p a r t on c o l l o i d s , there was no l i n e a r r e l a t i o n s h i p between v i s c o s i t y and molecular weight of any s o l u t i o n . Mark, a t the I . G. Farben Ludwigschafen l a b o r a t o r y , became c u r i o u s about the p o s s i b i l i t y of such a r e l a t i o n s h i p i n 1927. His i n t e r e s t was more than passing as f i b e r p r o d u c t i o n at I . G. Farben was commonly p r a c t i c e d i n the f a c t o r i e s by s p i n n i n g from high v i s c o s i t y s o l u t i o n s . This a p p l i c a t i o n r e s u l t e d i n s e v e r a l s c i e n t i s t s being assigned the study of the r h e o l o g i c a l behavior of s o l u t i o n s . I t was only n a t u r a l that Mark, from the vantage of the c o o r d i n a t o r of s e v e r a l groups, n o t i c e the r e l a t i o n s h i p . The p r a c t i c a l nature of the s t u d i e s p r e r e q u i s i t e d slow p u b l i c a t i o n of the f i n d i n g s . Towards the middle of 1929, Mark was c l e a r l y c l o s e to e s t a b l i s h i n g a v i s c o s i t y equation. He and H. F i k e n t s c h e r published a somewhat complex r e l a t i o n s h i p of v i s c o s i t y , and molecular volume (33). I t was based on the E i n s t e i n r e l a t i o n ship of v i s c o s i t y and s o l u t e c o n c e n t r a t i o n . At about the same time, Staudinger d e r i v e d h i s w e l l known "law of v i s c o s i t y " . His work was formulated i n 1929 and published i n 1930 (3*4, 35). A l s o based on the E i n s t e i n r e l a t i o n s h i p , Staudinger's equation was a d i r e c t r e l a t i o n s h i p between the s p e c i f i c v i s c o s i t y and the polymer molecular weight. η _ 0

= constant χ M

In d e r i v i n g h i s equation, Staudinger assumed the macromolecules were s t r a i g h t , r i g i d rods. T h i s assumption i s , w i t h h i n d s i g h t , wrong. I t s accuracy because of i n a c c u r a c i e s i s i r o n i c a l l y good. Use of Staudinger's assumptions r e s u l t s i n the use of a molecular volume which i s too h i g h . At the same time, molecules i n h i s model were expected to r o t a t e i n o n l y one plane. In reality r o t a t i o n may occur i n any plane, and t h i s l i m i t a t i o n r e s u l t s i n the use of too s m a l l a molecular volume. The a p p l i c a -



6.

STAHL

The

75

Geheimrat

b i l i t y of Staudinger's equation was, t h e r e f o r e , based on compen s a t i o n of the e r r o r s . In both Ludwigschafen and F r e i b u r g , work q u i c k l y s h i f t e d to determining molecular weight by v i s c o s i t y measurements a f t e r experimentally e s t a b l i s h i n g the r e l a t i o n s h i p . Staudinger's l a b o r a t o r y without the r e s t r i c t i o n s of p r a c t i c a l a p p l i c a t i o n published more f r e q u e n t l y . Mark only p u b l i s h e d on the s u b j e c t once again before l e a v i n g I . G. Farben i n 1932 (36). In Vienna i n the f a l l , Mark returned to the problem em p l o y i n g the same approach as when a t I . G. Farben. Summarized, he b e l i e v e d that molecules of such l a r g e dimensions were capable of assuming many d i f f e r e n t conformations through r o t a t i o n about valence bonds and had to be d e a l t with s t a t i s t i c a l l y j u s t as gases a r e . Convinced that he was " i n over h i s head" mathe m a t i c a l l y , he turned to a f e l l o w Viennese, H. T h i r r i n g , f o r a d v i s e . T h i r r i n g recommended Eugene Guth. In 1933 and 1934, Guth and Mark (37, 38) and Kuhn (39) independently s t u d i e d the problem and a r r i v e d a t s i m i l a r solutions. These i n v e s t i g a t i o n s f u r n i s h e d the background necessary to more c l e a r l y d e f i n e the r e l a t i o n s h i p of molecular weight and high v i s c o s i t y . In the f o l l o w i n g four years Mark s u c c e s s i v e l y r e p o r t e d on the v i s c o s i t y and molecular weight of c e l l u l o s e (40), S t a u d i n ger's Law (41), high polymer s o l u t i o n s (42), and the e f f e c t o f v i s c o s i t y on p o l y m e r i z a t i o n r a t e s (43). Confident of h i s f i n d i n g s , he proposed (at the same time as R. Houwink) the general v i s c o s i t y equation now known as the Mark-Houwink Equation (44, 45). ^sp

=

constant χ M

a

Mark and Houwink were the f i r s t to formulate the equation i n the power form and to demonstrate i t s v a l i d i t y by means of e m p i r i c a l v a l u e s . I n r e a l i t y , the Mark-Houwink Equation i s simply the E i n s t e i n v i s c o s i t y equation, which assumed spheres, t r a n s f e r r e d t o p a r t i c l e s with s i z e dependent p a r t i c l e d e n s i t y . The importance o f the equation cannot be dismissed as simply. Since i t s p u b l i c a t i o n , a great d e a l of use has been made of s o l u t i o n v i s c o s i t y measurements, and a l a r g e l i t e r a t u r e has grown up around i n t e r p r e t a t i o n o f the measurements. I t i s probably s a f e to say that no one working i n the research or development of e i t h e r n a t u r a l or s y n t h e t i c polymers w i l l not a t one time or another, knowingly or unknowingly, use the equation. One of the e a r l y goals of Mark and Staudinger, determination of molecular weight by v i s c o s i t y measurements, cannot be accom p l i s h e d i n an a b s o l u t e sense by t h i s method. "In A u s t r i a one has to (and always has had to) search f o r areas of r e s e a r c h f o r which the economic n e c e s s i t y i s


76

POLYMER SCIENCE

OVERVIEW

r e l a t i v e l y s m a l l . An example i s P r e g l and h i s microchemistry. Microchemistry i s a l o t cheaper than macrochemistry. H. F. Mark


11

Mark f a c e d a s t e r n c h a l l e n g e when he became D i r e c t o r of the First Chemistry I n s t i t u t e at the U n i v e r s i t y of Vienna i n the f a l l of 1932. Modernization of the l a b o r a t o r y equipment and teaching were new problems to be faced a l o n g s i d e h i s r e s e a r c h and a d m i n i s t r a t i v e r e s p o n s i b i l i t i e s . His toughest s i n g l e task, however, was b u i l d i n g a s u c c e s s f u l program of study i n a r e l a t i v e l y new, n o n - t r a d i t i o n a l f i e l d . His predecessor, Pro f e s s o r Rudolf Wegscheider, had l e d the I n s t i t u t e along the l e s s r a d i c a l l i n e s of c l a s s i c a l thermodynamics and k i n e t i c s . The area of study Mark advocated, polymers, was somehow l e s s acceptable. The f i e l d was new. F u r t h e r , i t was d i s c r e d i t e d by the intense debate raging between i t s advocates. I f not enough, the booming commercialization of polymeric m a t e r i a l s made the f i e l d l e s s f i t f o r "proper and r e s p e c t a b l e " study. Determined, Mark q u i c k l y and d i p l o m a t i c a l l y came to an agreement w i t h h i s Vienna c o l l e a g u e s . Speaking f i r s t to E.Spaeth, the Second Chemistry I n s . D i r e c t o r (and successor of W. Schlenk when the l a t t e r took Mark to B e r l i n i n 1921), then A. Franke, A. K a i l a n , V. Klemenc, and F. P o l l a k , he r e c e i v e d t h e i r guarded approval of h i s p l a n s . Then without delay, he launched a three pronged e f f o r t . His s t r a t e g y was simple. As a part of modernization, he would b r i n g q u a l i t y s c i e n t i s t s to the i n s t i t u t e , i n i t i a t e a s e r i e s of " s p e c i a l l e c t u r e s " presented by both s t a f f and v i s i t i n g s c i e n t i s t s , and concentrate r e s e a r c h i n the l e s s s t u d i e d area of p o l y m e r i z a t i o n mechanisms. Generously d i s p e r s i n g r e s e a r c h funds r e c e i v e d from I . G. Farben, the A u s t r i a n M i n i s t r y of Education, and the U n i v e r s i t y , Mark soon assembled a group of s k i l l e d and motivated s c i e n t i s t s . A l i s t of these a s s o c i a t e s i n c l u d e s p h y s i c i s t s E. Broda, Ε. Guth, and R. Simha; p h y s i c a l chemists F. E i r i c h , P. Gross, 0. Kratky, F. P a t a t , E. Suess, and H. Tschamler; and organic chemists J . W. Breitenbach, H. D o s t a l , R. R a f f , and A. von Wacek. These s c i e n t i s t s took over r e s p o n s i b i l i t i e s as the program grew, slowly f r e e i n g Mark. As a r e s u l t of good manage ment of t a l e n t e d a s s o c i a t e s , Mark's a c t i v i t i e s at Vienna were no l e s s d i v e r s e than i n Ludwigschafen and d e f i n i t e l y i n t e r nationally flavored. His plan to concentrate research i n the area of polymeriza t i o n mechanisms was i n the beginning more requirement than c h o i c e . On a r r i v i n g i n Vienna, Mark q u i c k l y r e a l i z e d that l e s s experienced hands could not prepare monomers and polymers at the speed and p u r i t y necessary to compete w i t h the Ludwigschafen and F r e i b u r g l a b o r a t o r i e s . Thus e a r l y on, r e s e a r c h was d i r e c t e d toward observing p o l y m e r i z a t i o n , c o p o l y m e r i z a t i o n , and r e a c t i o n



STAHL

The

Geheimrat

Figure 4. Professor Herman Mark and models of flexible (Mark) and rigid (Staudinger) macromolecules. The photograph was taken in Brooklyn on October 21,1979.

Figure 5. Several members of the First Chemistry Institute in Vienna in 1934. (left to right) C. Rogowin, H. F. Mark, Mark's sister Elizabeth, I. Saito, and E. Guth.


78


rate characteristics. During the f i r s t years work centered about r e c o r d i n g data, d e l a y i n g i n t e r p r e t a t i o n of the r e s u l t s . Inter p r e t a t i o n began i n the mid-1930's by which time the I n s t i t u t e and i t s personnel were ready. They were by the l a t e 1930 s considered among the best i n the world. In Vienna, Mark published a number of fundamental papers. T h e i r t o p i c s i n c l u d e p o l y m e r i z a t i o n mechanism (46, 47, 48), thermal p o l y m e r i z a t i o n (49, 50), p o l y m e r i z a t i o n k i n e t i c s (51), the e f f e c t of oxygen on p o l y m e r i z a t i o n (52), and measurement of molecular weight d i s t r i b u t i o n (53). Guth and Mark expanded t h e i r modeling of extended and b a l l e d thread molecules to i n clude rubber. The r e s u l t of t h e i r s t u d i e s was a s e r i e s of v e r y important papers i n which the thermal e f f e c t on expansion and r e l a x a t i o n of rubber i s explained (54, 55, 56). I n c r e d i b l y , a review of Mark's p u b l i c a t i o n s a l s o shows that he authored s i x papers on s u r f a c e c h a r a c t e r i s t i c s and dying, f i v e on the X-ray s t r u c t u r e of c e l l u l o s e and polymers, four on X-ray d i f f r a c t i o n ( i n c l u d i n g one on the s t r u c t u r e s of CII+ and CBr^), and twelve review papers. In a l l Mark c o n t r i b u t e d to more than seventy papers. More impressive, he penned s i x books w h i l e at the U n i v e r s i t y of Vienna. Two of h i s books, "Roentgenographic Untersuchung von K r i s t a l l e n " coauthored by F. H a l l a (57) and "Hochpolymere Chemie"coauthored by Κ. H. Meyer (58), were p a r t i c u l a r l y w e l l r e c e i v e d . A seventh book, " P h y s i c a l Chemistry of High Polymeric Systems" (59) was w r i t t e n i n Vienna but not published u n t i l 1940. Mark's a c t i v i t i e s i n Vienna were not l i m i t e d to r e s e a r c h and a d m i n i s t r a t i o n . During t h i s p e r i o d , he was appointed a member of the A u s t r i a n M i n i s t r y of Education, P r e s i d e n t of the Committee on Wood U t i l i z a t i o n , and a c o n s u l t a n t to the M i n i s t r i e s of Industry, A g r i c u l t u r e , and F o r e i g n R e l a t i o n s . The a p p o i n t ments were made by Engelbert D o l l f u s s , a wartime comrade of h i s , who became f i r s t C h a n c e l l o r i n 1932 and l a t e r a n t i - N a z i strong man of A u s t r i a . In a d d i t i o n , he served on the l o c a l avalanche squad and wrote s e v e r a l a r t i c l e s on p r e d i c t i o n of avalanches. He climbed g l a c i e r s searching f o r a new source of D2O and kicked with the F i r s t Chemistry's f o o t b a l l team. Again, as i n Germany, the changing p o l i t i c a l s i t u a t i o n l e d to a turning p o i n t i n h i s l i f e . D o l l f u s s was a s s a s s i n a t e d i n 1934, and the N a z i s pushed i n earnest f o r c o n t r o l . Mrs. Mark saw c l e a r l y what these events harbingered, but the e f f e r v e s c e n t , o p t i m i s t i c Mark d i d not. He continued h i s d i v e r s e a c t i v i t i e s undaunted, u n t i l l a t e 1937. F i n a l l y , at the u r g i n g of Mrs. Mark he agreed to i n v e s t i g a t e o p p o r t u n i t i e s o u t s i d e of A u s t r i a . One such c o n t a c t was made i n the f a l l when C. B. Thome, T e c h n i c a l D i r e c t o r of the Canadian I n t e r n a t i o n a l Paper Co., v i s i t e d Europe. Mark and Thorne a t Thome's i n v i t a t i o n met i n Dresden. They discussed Mark j o i n i n g the company s t a f f as Manager of Research. Thorne r e a l i z e d that the company l a b o r a t o r i e s had been outdated by the r e c e n t developments i n polymer


T



6.

STAHL

The

Geheimrat

79

science. His hope was to o b t a i n the necessary l e a d e r s h i p to modernize the f a c i l i t i e s by b r i n g i n g Mark, a leader i n those developments, to Ontario. Mark, hopeful of improvement i n the p o l i t i c a l c l i m a t e of A u s t r i a , n e i t h e r accepted nor d e c l i n e d the offer. In a ploy f o r time, he suggested an a l t e r n a t i v e one year appointment to s t a r t the f a l l of 1938. Mark returned to Vienna, and Thorne completed h i s European tour. Thorne returned to Canada convinced that Mark was the r i g h t man to lead Canadian I n t e r n a t i o n a l e modernization. Unfortunately, the p o l i t i c a l developments i n Vienna grew darker. T h e i r e f f e c t s could by then be f e l t by the whole s c i e n t i f i c community. U n t i l that time, the chemistry department was s a f e l y ensconced i n a b u i l d i n g a kilometer from the p o l i t i c a l forum a t the center u n i v e r s i t y . However, by December, 1937, the " a r r i v a l of H i t l e r " was no longer doubted by even the most optimistic. The b r i g h t e s t view was that the r e p r e s s i o n would not be as severe i n A u s t r i a " s i n c e the Nazis were no longer threatened". Immediate e f f e c t s on research were reduced funds and fewer students. By then, even the garrelous Mark grew r e t i c e n t as he recognized the r a m i f i c a t i o n s . Mark knew i n e a r l y 1938 t h a t h i s emigration was necessary. At that time he began to delegate a d m i n i s t r a t i v e d u t i e s to i n d i v i d u a l s a t the I n s t i t u t e who would stay. This s e l f l e s s duty, p a i n f u l as i t must have been, prepared the I n s t i t u t e f o r the d i f f i c u l t i e s ahead, but the p r e p a r a t i o n was s u c c e s s f u l . As one a s s o c i a t e s a i d , "Mark l e f t a w e l l appointed and o r d e r l y house". Hopes and p r e p a r a t i o n s almost delayed Mark's departure too long. German troops occupied A u s t r i a sooner than expected. They entered Vienna on March 15, 1938. Mark was a r r e s t e d the f o l l o w i n g day, and r e t a i n e d i n the Hotel M e t r o p o l i t a n . After four days of q u e s t i o n i n g , he was r e l e a s e d without h i s passport and with a s t e r n warning not to have contact with anyone Jewish. During the next e i g h t weeks, he r a r e l y s l e p t at home i n order to avoid the p e r i o d i c n i g h t v i s i t s by the Gestapo. Time, f o r Mark and many others faced with Nazi c o n t r o l , suddenly became p r i c e l e s s . Mark surmised he had to q u i c k l y s o l v e three problems. They were: contact Thorne i n Canada and secure the p o s i t i o n he o f f e r e d and h i s a s s i s t a n c e i n o b t a i n i n g a Canadian v i s a , get h i s A u s t r i a n passport back, and withdraw as much money as p o s s i b l e without drawing adverse a t t e n t i o n . Thorne q u i c k l y confirmed the o f f e r and solved the v i s a problem by o b t a i n i n g the s i g n a t u r e of the Canadian ambassador. A Swiss v i s a came e a s i l y w i t h the Canadian v i s a i n hand. Return of the passport was more d i f f i c u l t . Mark solved i t by appealing to a Nazi lawyer (and former schoolmate) to p e t i t i o n f o r i t f o r him. This step was necessary s i n c e Mark was not allowed to act on h i s own b e h a l f . A liberal application of the t h i r d i n g r e d i e n t , money, brought the document home. The money problem was handled d i s c r e t e l y by Mark, the s c i e n t i s t .


80



He bought over 1100g of p l a t i n u m / i r i d i u m from a number of suppliers. The wire was bent i n t o coat hangers. A f t e r e i g h t harrowing weeks, the Mark family—Herman, Mimi, t h e i r two boys, and a niece, strapped s k i s , p i c k s , and ropes to the top o f t h e i r c a r and hung a Nazi f l a g on the r a d i a t o r . They drove i n t o Switzerland on May 10, 1938. "There are no workers i n the world ( i n polymer s c i e n c e ) who at some point i n t h e i r i n v e s t i g a t i o n s a r e not indebted to h i s p i o n e e r i n g work." E r i c Rideal "None of the b i g American u n i v e r s i t i e s a t that time had a department f o r polymers. There was only Marvel a t I l l i n o i s . It was a d i f f i c u l t beginning, but i t was lucky f o r Speed and me. In America everything s t i l l depends on having something others don't have." H. F. Mark When Mark and h i s f a m i l y a r r i v e d i n Z u r i c h i n May of 1939, they immediately n o t i f i e d the Canadian I n t e r n a t i o n a l Paper Company, Manager of Research, Sigmond Wang. Anxious to help, Mr. Wang arranged t h e i r passage to Canada i n such d e t a i l that they were a b l e to spend the summer v i s i t i n g f r i e n d s and t o u r i n g l a b o r a t o r i e s . The Mark f a m i l y passed May i n S w i t z e r l a n d , June i n France, and July-August i n England. Near mid-September Mark embarked f o r a new p o s i t i o n i n the q u i e t e r surroundings of Hawkesbury, O n t a r i o . Two months l a t e r i n November, Mrs. Mark followed with t h e i r two sons and household goods which they " b r i b e d " out of A u s t r i a . In Hawkesbury, Mark found the s t a t e of the l a b o r a t o r y j u s t as Thorne and Wang had d e s c r i b e d . The l a b o r a t o r y equipment was outdated, and the s c i e n t i s t s were employing the o l d e r , c o n v e n t i o n a l , e m p i r i c a l methods. C l e a r l y , the l a b o r a t o r y was w e l l behind i n the p r i n c i p l e s and procedures advocated by the new schools of high molecular weight chemistry i n Europe. Even Mark, who was very w e l l known throughout Europe, r e q u i r e d i n t r o d u c t i o n . Yet, d e s p i t e these problems, modernization of the l a b o r a t o r i e s was not d i f f i c u l t . Above i t a l l , Mark was greeted by e n t h u s i a s t i c , i n q u i s i t i v e coworkers and s u f f i c i e n t c a p i t a l to i n i t i a t e the r e q u i r e d changes. On a r r i v a l , he found that h i s d u t i e s were not l i m i t e d s o l e l y to modernization of the Hawkesbury l a b o r a t o r y . He was a l s o charged w i t h s u p e r v i s i o n of the pulp q u a l i t y c o n t r o l l a b o r a t o r i e s s c a t t e r e d i n a dozen paper m i l l s throughout Canada. Always the o p p o r t u n i s t , Mark used h i s frequent business t r a v e l s to i n i t i a t e contact with other s c i e n t i s t s and present l e c t u r e s .



6.

STAHL

The

Geheimrat

81

Mark returned to research a f t e r the modernization program was organized and operating smoothly. L i m i t e d to c e l l u l o s e chemistry by the n e c e s s i t y of commercial f e a s i b i l i t y , he studied c e l l u l o s e a c e t a t e and the e f f e c t of the degree of a c e t y l a t i o n on product s o l u b i l i t y . At the same time he worked c l o s e l y on the development of s u i t a b l e a n a l y t i c a l methods to measure molecular weight d i s t r i b u t i o n and the degree of f u n c t i o n a l i t y . The most important problem to be solved i n Hawkesbury was how to improve the q u a l i t y of wood pulp so that i t could be used i n the production of rayon t i r e cords. The problem was p a r t i c u l a r l y important s i n c e Canadian I n t e r n a t i o n a l Paper was the major s u p p l i e r of c e l l u l o s e to the l a r g e s t rayon manufac t u r e r i n the hemisphere, Ε. I. duPont, Mark and h i s a s s o c i a t e s found that two c o n d i t i o n s were c r u c i a l f o r strength and f a t i g u e of the yarn, namely near complete absence of i m p u r i t i e s ( r e s i n , l i g n i n , ash) and a narrow molecular weight d i s t r i b u t i o n of the c e l l u l o s e . Under Mark's tutorage, the s c i e n t i s t s i n Hawkes bury expanded the c l a s s i c a l methods f o r i s o l a t i o n of «(-cellulose and introduced an improved xanthate-Cu(NH3)^ v i s c o s i t y r e l a t i o n s h i p . Mark's broad knowledge and uncanny a b i l i t y to make the complicated or confused simple was i n a l a r g e p a r t r e s p o n s i b l e f o r t h e i r successes. When he a r r i v e d i n Canada i n 1938, he recognized the acute need f o r a l i t e r a t u r e - b o o k s i n p a r t i c u l a r - i n the Americas. S e i z i n g the opportunity he met with h i s former a s s o c i a t e and p u b l i s h e r E. S. Proskauer i n Montreal on a c o l d morning i n January, 1939. Proskauer, who had f l e d Germany i n 1937 and was l i v i n g i n New York, was the Chief Science E d i t o r a t I n t e r s c i e n c e P u b l i s h e r s . Walking s e v e r a l miles i n the snow, Mark and Proskauer conceived the I n t e r s c i e n c e High Polymer S e r i e s . They agreed to i n i t i a t e the s e r i e s by p u b l i s h i n g a c o l l e c t e d volume of the papers of Wallace H. Carothers (60). The High Polymer S e r i e s grew from t h i s conception to become one of the b e t t e r known and more important polymer source works. Despite Mark's d i v e r s e activités as a manager, l e c t u r e r , researcher, author, and e d i t o r , the i s o l a t i o n of l i v i n g i n Hawkesbury was too quiet f o r such a gregarious person. Restl e s s , he i n v e s t i g a t e d the p o s s i b i l i t y of o b t a i n i n g a p o s i t i o n i n the United States a t the 1939 f a l l meeting of the American Chemical S o c i e t y i n Baltimore. A scramble ensued f o r h i s s e r v i c e s among s e v e r a l American f i r m s . One f i r m , duPont, o f f e r e d him a p o s i t i o n as a consultant i n i t s Rayon Department and agreed to a s s i s t him i n o b t a i n i n g an academic p o s i t i o n and s t a t u s as a permanent r e s i d e n t . A short time afterward, assured by duPont's o f f e r of support, Dr. Harry Rogers, President of the P o l y t e c h n i c I n s t i t u t e of Brooklyn (now c a l l e d the P o l y t e c h n i c I n s t i t u t e of New York), o f f e r e d Mark a p o s i t i o n as an Adjunct P r o f e s s o r . "Canadian I n t e r n a t i o n a l , " Mark says, "was not p a r t i c u l a r l y e n t h u s i a s t i c about the p r o p o s a l , but


82


condescended i n view of t h e i r business r e l a t i o n s h i p w i t h du Pont. Mark and h i s f a m i l y l e f t Hawkesbury l a t e i n May of 1940. In 1940 most of the s h e l l a c imported i n t o the United States came i n through the docks of Brooklyn. I t was, there f o r e , appropriate that W. H. Gardner had s e l e c t e d the P o l y technic as the s i t e to e s t a b l i s h a n a t i o n a l t e s t i n g l a b o r a t o r y a few years before. Research at the l a b o r a t o r y , c a l l e d the S h e l l a c Bureau, centered on e v a l u a t i n g the p r o p e r t i e s of t h i s important n a t u r a l r e s i n . On assuming h i s p o s i t i o n i n Brooklyn, Mark was assigned to the S h e l l a c Bureau. Encouraged by Mark, Gardner q u i c k l y agreed that the research of the S h e l l a c Bureau should be expanded to i n c l u d e a study of s y n t h e t i c c o a t i n g s . Students were brought i n to work on these expanded p r o j e c t s . The presence of students convinced Mark that h i s most important s i n g l e task was to e s t a b l i s h a complete c u r r i c u l u m of study of polymer chemistry and technology. The teaching of students began that f a l l . The f i r s t course, taught by Mark, was "General Polymer Chemistry". Establishment of the program made "Brooklyn P o l y " the f i r s t u n i v e r s i t y i n the United States to o f f e r a degree i n polymer s c i e n c e . "The beginning was not easy," Mark e x p l a i n s , "but r e l a t e d experience i n Vienna and the p e e r l e s s support of Rogers and (Dean R. E.) K i r k made the I n s t i t u t e a quick success." The success was a l s o i n part brought about by the l a b o r s of a f u t u r e "who's who" contingent of a s s o c i a t e s a t t r a c t e d by Mark. A few of the s c i e n t i s t s who came to work i n the con v e r t e d r a z o r blade f a c t o r y which housed the P o l y t e c h n i c l a b o r a t o r i e s are T. A l f r e y , P. M. Doty, F. E i r i c h , I. Frankuchen, W. P. Hohenstein, H. Morawetz, C. G. Overberger, C. C. P r i c e , R. Simha, Α. V. Tobolsky, and Β. H. Zimm. Mark, r e a l i z i n g that the P o l y t e c h n i c was surrounded by numerous i n d u s t r i a l o r g a n i z a t i o n s , sought i n those f i r s t years a method to encourage s c i e n t i f i c and t e c h n i c a l i n t e r change between them and h i s growing department. He was s u c c e s s f u l i n h i s e f f o r t on a s c a l e beyond h i s hopes. This was accomplished by two innovations. F i r s t , he e s t a b l i s h e d a s e r i e s of r e g u l a r symposia to be h e l d each Saturday from October to May. A c t i v e areas of r e search and timely subjects were presented and discussed at these meetings. The s e r i e s , c a l l e d the "Saturday Symposia" as the years passed, were widely known and w e l l attended. A d d i t i o n a l p r e s t i g e was given the s e r i e s by the d i s t i n g u i s h e d f o r e i g n v i s i t o r s who, drawn by Mark's r e p u t a t i o n , o f t e n served as chairmen, speakers, and d i s c u s s i o n l e a d e r s . The net impact was to b r i n g the exposure necessary to e s t a b l i s h the department as the n a t i o n a l leader i n polymer s c i e n c e and g i v e i t i n t e r national recognition.


11



6.

STAHL

The

Geheimrat

83

The second v e h i c l e f o r c l o s e r cooperation between the department and i n d u s t r y was h i s e s t a b l i s h i n g " S p e c i a l Summer Courses". The courses which were the r e s u l t of a scheme by Mark and an a s s o c i a t e , I. Fankuchen, served an a n c i l l a r y purpose. The funds obtained by c o l l e c t i n g fees from the attendees were placed i n a s p e c i a l t r a v e l fund reserved f o r the f a c u l t y . A t y p i c a l course c o n s i s t e d of a l i m i t e d number of v i s i t i n g s c i e n t i s t s who remained at the P o l y t e c h n i c f o r a p e r i o d of one or two weeks. While there, they were given i n t e n s i v e t h e o r e t i c a l and experiment a l i n s t r u c t i o n i n a s p e c i a l area of the d i s c i p l i n e . The f i r s t courses were taught i n the summer of 1943 by Mark and a number of h i s a s s o c i a t e s i n c l u d i n g Fankuchen and H. S. Kaufman (X-ray c r y s t a l l o g r a p h y ) , and T. A l f r e y , P. M. Doty, and Β. H. Zimm (molecular weight). Mark was named D i r e c t o r of the S h e l l a c Bureau i n 1941 when W. H. Gardner was c a l l e d to Washington, D.C. on government work. Under Mark's l e a d e r s h i p r e s e a r c h was expanded from s h e l l a c to s y n t h e t i c c o a t i n g s and e v e n t u a l l y to the p r e p a r a t i o n , p r o p e r t i e s , and p o l y m e r i z a t i o n mechanism of a v a r i e t y of s y n t h e t i c polymers. Research by the end of World War I I had f a r outgrown the S h e l l a c Bureau. In 1946, Mark guided a r e o r g a n i z a t i o n of the polymer e f f o r t and thus was instrumental i n c r e a t i o n of the now famous Polymer Research I n s t i t u t e . At the same time another long-time goal of Mark's was r e a l i z e d . Simultaneous with formation of the I n s t i t u t e , the P o l y t e c h n i c i n i t i a t e d a course of study l e a d i n g to a degree of Doctor of Philosophy i n Polymer Chemistry. Government spending during the Second World War and i n the c o l d war years afterward provided a boom to Mark and the I n s t i t u t e . A number of l a r g e and important p r o j e c t s were sponsored a t the I n s t i t u t e i n the area of s y n t h e t i c f i b e r s , f i l m s , and rubber by the OSRD, ONR, and other U.S. Government agencies. The work a t P o l y t e c h n i c d i d not only c o n t r i b u t e to the goal of the p r o j e c t s , but a l s o to numerous p u b l i c a t i o n s i n s c i e n t i f i c j o u r n a l s . The combined output of the Polymer Research I n s t i t u t e and s e v e r a l other r a p i d l y growing polymer r e s e a r c h e f f o r t s such as that of C. S. Marvel i n Urbana, IL soon caused a b o t t l e n e c k of p u b l i c a t i o n s . When Carothers began h i s s t u d i e s i n 1928 a great d e a l of the American chemical r e s e a r c h was reported i n the J o u r n a l of the American Chemical S o c i e t y (JACS). The arrangement was s a t i s f a c t o r y f o r more than a decade, but with the sudden i n c r e a s e i n the number of p u b l i c a t i o n s , A. Noyes, e d i t o r of JACS, became l e e r y of accepting too many polymer manuscripts. Mark's r e a c t i o n was to approach Noyes about the American Chemical S o c i t y s t a r t i n g a j o u r n a l on polymer chemistry. Noyes, however, r e j e c t e d the idea s i n c e the number of papers, about a hundred per year, was regarded as too small to merit a separate journal. Mark then turned to the ubiquious I n t e r s c i e n c e e d i t o r , E r i c Proskauer. Together, they founded the J o u r n a l of Polymer Science. The j o u r n a l was not i n the e a r l y going as p r o f i t a b l e



84

POLYMER SCIENCE

OVERVIEW

as they would have p r e f e r r e d , but w i t h i n a few years the volume of papers and s u b s c r i b e r s increased a great d e a l . The j o u r n a l became so a c t i v e that i n 1953 i t was branched to i n c l u d e the J o u r n a l of A p p l i e d Polymer Science. Even t h i s second j o u r n a l was not enough. Within ten years the o r i g i n a l p u b l i c a t i o n was s p l i t i n t o chemistry, p h y s i c s , and l e t t e r s s e c t i o n s . Mark, the founder, serves to t h i s day as an e d i t o r of both j o u r n a l s . Most of Mark's Brooklyn a s s o c i a t e s w i l l r e a d i l y t e s t i f y that the guidance, teaching, and encouragement rendered by the c h i e f was i n v a l u a b l e i n t h e i r a t t a i n i n g personal and research g o a l s . T h e i r c o l l e c t i v e success and t h i s compliment i s not s u r p r i s i n g when Mark's unique l i f e l o n g t a l e n t f o r l e a d i n g i s considered. The breadth of t h e i r research s i m i l a r l y r e f l e c t s h i s d i v e r s e i n t e r e s t s and a b i l i t i e s . S c i e n t i f i c a l l y , the r e s e a r c h a t the I n s t i t u t e was a c o n t i n u a t i o n of the Mark d i r e c t e d programs i n Vienna and, to a l e s s e r extent, i n Hawkesbury. Yet the Brooklyn r e s e a r c h was improved by b e t t e r instrumentation, refinement i n techniques, and a unique a l l i a n c e o f s c i e n t i s t s w i t h a broad range of experiences. Since j o i n i n g the P o l y t e c h n i c , Mark has w r i t t e n over three hundred r e s e a r c h papers, r e l a t e d a r t i c l e s and books. A l i s t f a r too long to be reviewed i n t h i s s e c t i o n ; however, a l i s t should c o n t a i n s e v e r a l outstanding items. S e v e r a l books were w r i t t e n i n c l u d i n g " P r i n c i p l e s o f the P h y s i c a l Chemistry of High Polymeric Systems" with Α. V. Tobolsky (61) and "High Polymeric R e a c t i o n s " with R. Raff (62). A d e t a i l e d , systematic study of the i n f l u e n c e of c o n c e n t r a t i o n , s o l v e n t , c a t a l y s t s , and temperature on v i n y l a d d i t i o n p o l y m e r i z a t i o n was conducted. Polymer f r a c t i o n a t i o n techniques were improved and extensive use was made of osmometry, viscometry, and X-ray a n a l y s i s . Related important research was i n i t i a t e d with Mark's a s s i s t a n c e and encouragement. A l i s t of these p r o j e c t s i n c l u d e s the use of r a d i o a c t i v e bromine end group l a b e l s ; hydrogen-deuterium exchange r a t e measurements; the r a t e of d i f f u s i o n of vapors through polymer f i l m s ; and the consequences of molecular o r i e n t a t i o n , c r y s t a l l i n i t y , p l a s t i c i z e r content, and temperature ( t h i s l a t t e r study l e d to the d i s c o v e r y o f the "soc a l l e d Second Order Glass T r a n s i t i o n P o i n t " ) . Other p r o j e c t s of s p e c i a l i n t e r e s t to Mark i n c l u d e d A l f r e y and G o l d f i n g e r ' s develop ment of a copolymer composition equation, and the A l f r e y - P r i c e Q-e scheme. A t i m e l y , comprehensive t r e a t i s e of the copolymeri z a t i o n f i e l d was published i n Volume VIII of the High Polymer S e r i e s as " c o p o l y m e r i z a t i o n " by T. A l f r e y , J . J . Bohrer, and H. Mark (63). Throughout the years, i t has been customary that P r o f e s s o r s at the I n s t i t u t e pursue t h e i r own r e s e a r c h p r o j e c t s with the a s s i s t a n c e of the younger members and i n c l o s e c o o r d i n a t i o n with Mark. Among the p r o j e c t s conducted by these P r o f e s s o r s under Mark's i n f l u e n c e between 1940 and 1960 a r e T. A l f r e y ' s study of mechanical p r o p e r t i e s , R. B. Mesrobian on g r a f t copolymerization, M. Goodman on the stereochemistry of polymers, F. R. E i r i c h on



6.

STAHL

The

Geheimrat

85

rheology, G. Oster on photochemistry of polymers, H. P. Gregor on p o l y e l e c t r o l y t e s , H. Morawetz on s o l i c s t a t e p o l y m e r i z a t i o n , and C. G. Overberger on the organic chemistry of monomers and polymers. The presence of a world reknown f i g u r e such as Mark i n a c i t y l i k e New York placed the Polymer Research I n s t i t u t e i n an e n v i a b l e p o s i t i o n . Taking f u l l advantage, Mark and, l a t e r , Overberger as head of the I n s t i t u t e always attempted to stay abreast of new developments by symposia, seminars, and the exchange of s c h o l a r s . The academic events, f o r example, during G. N a t t a s f i r s t v i s i t to the United States were organized a t the I n s t i t u t e . A. K e l l e r presented one of the f i r s t r e p o r t s i n the United States on h i s d i s c o v e r y of chain f o l d i n g a t "Poly", and Max Perutz (whom Mark placed with B e r n a i i n 1936) v i s i t e d a f t e r r e c e i v i n g the Nobel P r i z e and presented the r e s u l t s of h i s hemoglobin s t u d i e s . C. V. Ramon came from I n d i a , L. Sakurada and S. Okamura from Japan, V. A. Kargin and A. Topchiev from Russia, K. Z i e g l e r from Germany, the Bergmans and Katschalskys from I s r a e l , Claesson and Rânby from Sweden and many other d i s t i n g u i s h e d s c i e n t i s t s from other c o u n t r i e s . Even Hermann Staudinger v i s i t e d the I n s t i t u t e i n 1953. (When given the "royal treatment by Mark, Staudinger was prompted to say, "Even Herman Mark now b e l i e v e s i n polymers!"). 1

11

Through h i s more than f o r t y years i n Brooklyn, Mark has been heaped with a c c l a i m , medals, and degrees. He r a i s e d h i s f a m i l y , and saw many sons both blood and academic go on to c a r e e r s . He has witnessed an expansion i n the s c i e n c e he helped c r e a t e which mocks those who disagreed with the concepts he and a t h i n l i n e advocated so many years ago. He has, as the years passed, a l s o encouraged the formation of new centers of r e s e a r c h which have a l s o d i l u t e d the i n f l u e n c e of " h i s " I n s t i t u t e . Perhaps the g r e a t e s t compliment of a l l i s t o p o i n t out that through i t a l l , i t was h i s s e l f l e s s encouragement of t h i s growth, h i s r e f u s a l to p r o t e c t personnel, h i s push to march away from Brooklyn and s t a r t new c e n t e r s , h i s w i l l i n g n e s s t o go out and l e c t u r e r a t h e r than "mind the s t o r e " which i s no small part r e s p o n s i b l e f o r the growth. In 1961, Mark was appointed Dean of the F a c u l t y of the P o l y t e c h n i c . A f t e r a s s i s t i n g i n the r e o r g a n i z a t i o n of the s t r u c t u r e of the I n s t i t u t e , he r e t i r e d i n 1964 and was appointed as a member of the Corporation of the P o l y t e c h n i c I n s t i t u t e and r e c e i v e d the t i t l e , Dean Emeritus of the F a c u l t y . The t i t l e Mark p r e f e r s was not given by the a d m i n i s t r a t o r s . On the o c c a s i o n of h i s s i x t i e t h b i r t h d a y i n 1955, h i s a s s o c i a t e s i n Brooklyn bestowed the t i t l e of "Geheimrat" on him. "Geheimrat", a t i t l e given to haughty, pompous p r o f e s s o r s i n the o l d German s c h o o l s , seemed q u i t e funny s i n c e i t embodied so much of what Mark was n o t . Yet, the name stuck to the d e l i g h t of a l l — e s p e c i a l l y "the Geheimrat".


86


Acknowledgement s The author g r a t e f u l l y acknowledges the cooperation of Drs. Ε. H. Immergut, H. Morawetz, C. G. Overberger, E. Proskauer, and e s p e c i a l l y the Geheimrat. They endured taped interviews and endless r e p e t i t i v e questions. S p e c i a l thanks i s due Dr. Claus P r i e s n e r f o r generously sharing h i s f i n d i n g s on the Staudinger-Meyer-Mark polemics. The information used by t h i s author i s presented i n r e f e r e n c e 27; however, Dr. P r i e s n e r s forthcoming book, "H. Staudinger, H. Mark, and Κ. H. Meyer — Thesen zur Groese und Struktur der Makromolekule", i s the most complete work on t h i s s u b j e c t .


T

Literature Cited 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. 22. 23.

Mark, H. Z. Angew. Chem., 1927, 40, 16; ibid, 1927, 40, 645; and ibid, 1927, 40, 1497. Kallman, H. and Mark, H. Z. Physik, 1926, 36, 120. Mark, H. and Schochen, K. Naturwissenschaften, 1927, 15, 139. Mark, H. J. Soc. Glass Tech., 1926, 11 (41), 54. Mark, H. Z. Metallkunde, 1928, 20, 342. Mark, H. Naturwissenschaften, 1928, 16, 892. Hengstenberg, J . and Mark, H. Z. Krist Miner., 1928, 69, 271. Meyer, Κ. H. and Mark, H. Ber., 1928, 61B, 1932. Meyer, Κ. H. and Mark, H. Ber., 1928, 61B, 1936. Meyer, Κ. H. and Mark, H. Ber., 1928, 61B, 1939. Meyer, Κ. H. and Mark, H. Ber., 1928, 61B, 593. Mark, H. and Susich, G. V. Z. Physik, 1930, 65, 253. Bergmann, E. and Mark, H. Ber., 1929, 62B, 750. Hengstenberg, J. and Mark, H. Z. Krist., 1929, 70, 283. Mark, H. and Wierl, R. Naturwissenschaften, 1928, 16, 725. Mark, H. and Wierl, R. Z. Physik, 1929, 53, 526; ibid, 1929, 55, 156; and ibid, 1929, 57, 494. Mark, H. and Wierl, R. Naturwissenschaften, 1930, 18, 205, 753, 778. Mark, H. and Wierl, R. Z. Physik, 1930, 60, 741. Mark, H. and Wierl, R. Z. Elektrochem., 1930, 36, 675. Hengstenberg, J. Chemie Kunststoffe Aktwell, 1980, 34(2), 23. Meyer, Κ. H. and Mark, H. "Aufbau der Hochpolymeren Substanzen"; Hirschwaldsthe Buchhandlung: Berlin, 1930; 240 pp.. Meyer, Κ. H. and Mark, H. "Der Aufbau der Hochpolymeren Organischen Naturstoffe"; Akad. Verlogsges: Leipzig, 1930; 264 pp.. Mark, H. and Wierl, R. "Die Experimentellen und Theoretischem Grundlagen der Elektronenbeugung"; Gebrueder Berntraeger: Berlin, 1930; 126 pp..


6. STAHL The Geheimrat

24.


25. 26. 27. 28. 29. 30. 31. 32. 33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48. 49. 50. 51. 52. 53. 54. 55. 56. 57. 58. 59. 60.

87

Mark, H. "Physik und Chemie der Cellulose" in Herzog, R. D. (Ed.) "Technologie der Textilfasern"; J. Springer: Berlin, 1932. Olby R. "The Path to the Double Helix"; University of Washington Press: Seattle, WA, 1974; p. 6. Staudinger, H. Ber., 1920, 53, 1073. Priesner, C. Chemie in unserer Zeit., 1979 (2), 43. Meyer, Κ. H. Z. Angev. Chem., 1938, 41, 935. Staudinger, H. Ber., 1928, 61, 2427. Meyer, Κ. H. Z. Angew. Chem., 1929, 42, 76. Staudinger, H. Z. Angew. Chem., 1929, 42, 77. Staudinger, H. Naturwis senschaften, 1929, 17, 141. Mark, H. and Fikentscher Kolloid Z., 1929, 49, 135. Staudinger, H. and Heuer, W. Ber., 1930, 63, 222. Staudinger, H. and Nodzu, W. Ber., 1930, 63, 721. Mark, H. Kolloid Z., 1930, 53, 32. Guth, E. and Mark, H. Ergbnisse exakt. Naturw., 1933, 12, 115. Guth, E. and Mark, H. Monatsh., 1934, 65, 93. Kuhn, W. Kolloid Z., 1934, 68, 2. Mark, H. Chimie and Industrie Spec. No. 788, 1934. Meyer, Κ. H. and Mark, H. Z. Elektrochem., 1934, 40, 728. Eirich, F. and Mark, H. Ergeb. exakt. Naturw., 1936, 15, 1. Dostal, H. and Mark, H. Osterr. Chem. Ztg., 1937, 40, 25. Mark, H. Der Feste Koerper, Leipzig, 1938, p. 103. Houwink, R. J. prakt. Chem., 1940, 157, 15. Dostal, H. and Mark, H. Z. Physik. Chem., 1935, B29, 299. Dostal, H. and Mark, H. Trans. Fara. Soc., 1936, 32, 54. Mark, H. Naturwissenschaften, 1937, 25, 753. Mark, H. and Raff, R. Z. Physik. Chem., 1936, B31, 275. Dostal, H., Mark, Η., and Raff, R. Ind. Eng. Chem., 1937, 29, 595. Dostal, H. and Mark, H. Angew. Chem., 1937, 50, 348. Dostal, H. and Mark, H. Oesterr. Chem. Zgt., 1937, 40, 50. Dostal, H. and Mark, H. Trans. Fara. Soc., 1937, 33, 350. Guth, E. and Mark, H. Oesterr, Chem. Ztg., 1937, 40, 304. Guth, E. and Mark, H. Naturwissenschaften, 1937, 25, 353. Guth, E. and Mark, H. Z. Elektrochem., 1937, 43, 683. Halla, F. and Mark, H. "Roentgenographische Untersuchung von Kristallen"; J. A. Barth: Leipzig, 1937. Meyer, Κ. H. and Mark, H. "Hochpolymere Chemie"; Akademische VerPagsgesellschaft: Leipzig, 1937; 345 pp. Mark, H. "High Polymers, Vol. II, Physical Chemistry of High Polymeric Systems:; Interscience Publishers: New York, 1940; 345 pp.. Mark, H. and Whitby, G. S. "High Polymers, Vol. I, The Collected Papers of Wallace H. Carothers"; Interscience Publishers: New York, 1940; 459 pp..


88



61. Mark, H. and Tobolsky, Α. V. "High Polymers, Vol. II, 2nd Ed., Principles of the Physical Chemistry of High Polymeric Systems"; Interscience Publishers: New York, 1950; 506 pp.. 62. Mark, H. and Raff, R. "High Polymers, Vol. III, High Polymeric Reactions"; Interscience Publishers: New York, 1941; 476 pp.. 63. Alfrey, T., Bohrer, J. J . and Mark, H. "High Polymers, Vol. VIII, Copolymerization"; Interscience Publishers: New York, 1952; 269 pp.. RECEIVED

August 10, 1981.


Polymer Science Overview - ACS Publications - American Chemical

Recommend Documents