As I stated in the last blog, the current posting will contain another example of where “Kennedy” stole an invention made previously by a famous scientist. Before getting to that particular case a little bit of digression is necessary to illustrate another “Kennedy” tactic. That tactic is obscuring or in many cases simply omitting facts. A prime example is work the “Kennedy” group did on the copolymerization of isobutene with β-pinene. As it turns out, Emil Ott (of Hercules) first patented the copolymerization of isobutene with β-pinene where the solvent was ethyl chloride and the Lewis acids were BF3 and AlCl3.1 Much latter the “Kennedy” group reinvestigated copolymerization of these two monomers, the only difference being the use of EtAlCl2 and lower polymerization temperatures.2-5 In two of “Kennedy’s” books,2,5 the reader is led to believe that successful copolymerization of these two monomers had not been effected until “Kennedy” came upon the scene. These two books appeared after a peer reviewed article3 and patent4 had been published. The article itself is quite interesting to make note of since its title “Poly(isobutylene-co-β-Pinene) A New Sulfur Vulcanizable, Ozone Resistant Elastomer by Cationic Isomerization Copolymerization” is very significant as it is purposely worded to be misleading. That is, this copolymer had already been disclosed almost 15 years prior to “Kennedy’s” work!
Since the latter two documents were proofed by outsiders they make mention of Ott’s prior art disclosure1 of such copolymerizations; however, without such intervention “Kennedy” apparently thought to pull a fast one (in his books) and convince the reader that he invented the copolymer. Another very interesting fact is that in all of the aforementioned “Kennedy” references2-5 “Kennedy” puts forth another falsehood. “Kennedy’s” lie is that EtAlCl2 gives rise to azeotropic copolymerization whereas he claims other Lewis acids (e.g., AlCl3) do not. A close look at “Kennedy’s” patent4 (e.g., Tables II & III) actually demonstrates that AlCl3 (i.e., the system originally described by Ott) not only gives rise to azeotropic copolymerization but that it does so at a much higher reaction temperature than “Kennedy’s” EtAlCl2 system! These falsehoods were accidentally discovered when I was researching terpenic resins and were first disclosed in a book chapter6 that I coauthored on the subject. So not only was one of “Kennedy’s” first inventions at U. Akron actually made by another researcher 15 years prior but “Kennedy” mislead people to believe this invention has actual benefit over Ott’s disclosure when in fact it is less beneficial because it is more energy intensive. It is unknown the exact amount of money wasted by U. Akron on “Kennedy’s” inventions but the author of this blog believes it well exceeds $ 1 million.
As following blog postings will show, a repetitive pattern emerges when one scratches the surface of “Kennedy” patents. This pattern is that much of what “Kennedy” has patented is prior art (i.e., someone else invented it and disclosed it prior to “Kennedy”). A prime example is work done in 1961 by Sinn, Winter, and Tirptiz.7 Most people in the polymer science community will recognize Sinn’s name since he and Kaminsky are credited with discovering that alkylaluminoxanes are useful activators for metallocenes and ushered in a new era (i.e., single site catalysis) in the polymer science field. In the aforementioned Sinn, Winter, and Tirpitz paper these researchers describe the cationic polymerization of styrene by initiator systems consisting of dialkylaluminum halide + hydrohalogen acid and trialkylaluminum halide + hydrohalogen acid. Despite this fact, some years latter “Kennedy” was able to patent these same initiator systems for cationic polymerization while at Esso Corp!8 Interestingly, “Kennedy” comes clean about their true origin, not only in several journal articles9,10 but also in one of his books (the reader must go to the section on styrene to find this).2 Still, prior to this batch of “Kennedy” patents, “Kennedy” again mentions in both his paper and book that Russian researchers11 also previously described initiator systems based on dialkylaluminum halide + Brønsted acid for inducing cationic polymerization. It is unknown how these “Kennedy” patents were allowed to issue when it is clear to even the most casual observer that previous researchers had already disclosed these initiator systems as being useful for effecting cationic polymerization. As we will see in other blog postings, “Kennedy” continues this pattern; however, the most interesting topic of all is yet to come.* That is, the mystery of “Kennedy’s” true identity and the conflicting story he provides surrounding his past…
* Please note that with the exception of my invention and that of P.V. Kurian all other instances involving “Kennedy’s” stealing of other people’s inventions and his obfuscation or complete omission of facts were inadvertently discovered during review of journal articles and/or the chemical patent literature. It is the belief of the author of this blog that the total number of inventions stolen by “Kennedy” is in the many tens of instances.
References:
(1) Ott, E. Terpene Resins U.S. Patent 2,373,706, 1945.
(2) Kennedy, J. P. Cationic Polymerization of Olefins: A Critical Inventory; John Wiley and Sons: New York, 1975; pp 99-100.
(3) Kennedy, J. P.; Chou, T. Poly(isobutylene-co-b-Pinene) a new Sulfur Vulcanizable, Ozone Resistant Elastomer by Cationic Isomerization Copolymerization Adv. Polym. Sci. 1976, 21, 1-39.
(4) Kennedy, J. P.; Chou, T. M. Process for the Preparation of Isobutylene/Beta-Pinene Copolymers U.S. Patent 3,923,759, 1975.
(5) Kennedy, J. P.; Marechal, E. Carbocationic Polymerization; John Wiley and Sons: New York, 1982; pp 1-510.
(6) Mathers, R. T.; Lewis, S. P. Monoterpenes as Polymerization Solvents and Monomers in Polymer Chemistry.; In Green Polymerization Methods: Renewable Starting Materials, Catalysis and Waste Reduction; Mathers, R. T., Meier, M. A. R., Eds.; Wiley-VCH: New York, 2011; pp 91-128.
(7) Sinn, H. J.; Winter, H.; Tirpitz, W. V. Polymerisations- und Isomerisierungsaktivitat von Aluminiumtrialkyl, Alkylaluminiumhalogeniden und Ziegler-Mischkatalysatoren Makromolekulare Chemie 1961, 48, 59-71.
(8) Kennedy, J. P. Butyl Rubber Catalyst System Utilizing AlR2X with an HX Promoter U.S. Patent 3,349,065, 1967.
(9) Kennedy, J. P. Olefin Polymerizations and Copolymerizations with Aluminum Alkyl-Cocatalyst Systems. I. Co-catalysis with Bronsted Acid Systems J. Polym Sci., Part A-1 1968, 6, 3139-3150.
(10) Kennedy, J. P.; Gillham, J. K. Cationic Polymerization of Olefins with Alkylaluminum Initiators Adv. Polym. Sci. 1972, 10, 1-33.
(11) Tinyakova, E. I.; Zhuravleva, T. G.; Kurengina, T. M.; Kirikova, N. S.; Dolgoplosk, B. A. Dokl. Akad. Nauk 1962, 144, 592.