University of Akron/Professor Joseph P. Kennedy Expose, Part 19

The following example is one involving “Kennedy’s” almost exact copycatting of another researcher’s work.  If one takes a close look at the research reported by “Kennedy” they can come to a very quick conclusion of what the standard modus operandi is.  That is, conducting work almost identical to that of other investigators and/or stealing the ideas of others.*  From the foregoing blog posts it is obvious that a third track used by this individual is to falsify research data.  In regards to this latter strategy I was told that a female American student of his (who graduated around the time I was dismissed by “Kennedy” for refusing to falsify data) had in fact falsified the majority of experiments used in her dissertation.**  Subsequent blog postings will provide specific examples of ideas stolen by “Kennedy” and the copycatting aspect will only be secondary in terms of importance.

Recent “Kennedy” Copycatting Example

The area of using perfluoroarylated Lewis acid (PFLA) based initiators has been one of intense activity, especially during the 1990s up until recently.1-46  One of the early innovators in this field is Dr. Tim Shaffer of Exxon Mobil who developed a number of PFLA based initiator systems for the polymerization of isobutene (IB).  One of the initiator systems Shaffer devised was based upon the salt [Et3Si]+[B(C6F5)4] which is formed by hydride abstraction from a silane (i.e., Et3SiH) by [Ph3C]+[B(C6F5)4].40,42,43  This chemistry is well known (i.e., the driving force is formation of a stronger C-H bond from a weaker Si-H bond); however, it wasn’t until recently that such salts were shown to typically contain coordinated Et3SiH.47  Regardless, this system devised by Shaffer is one of very few initiator systems based on silanes for initiation of cationic polymerization.  Shortly after Shaffer’s disclosures (almost within the exact time frame) “Kennedy” reports an identical initiator system (i.e.,[Et3Si]+[B(C6F5)4]);15,16,36 however, in this instance [Et3Si]+[B(C6F5)4] is generated in situ via the metathesis reaction between Li[B(C6F5)4] and Et3SiCl (in this case the triethylsilylium tetrakis(pentafluorophenyborate) salt is formed along with LiCl)!!!  I can assure you that Zhengjie Pi (aka, Jack) was intimately involved in devising this system.***  Even those readers who are not trained chemists will realize the chemical identity of the initiator system reported by “Kennedy” is identical to that originally invented by Shaffer and only differ slightly in the way that the ion pair is generated.  The likelihood of “Kennedy” developing an almost identical initiator system independently and at the same time as Shaffer is about the same as the reader winning the Powerball lotto jackpot, especially given the scarcity of Si based initiator systems for cationic polymerization.****


* In later blog postings we are going to see that “Kennedy” not only has a habit of stealing ideas, but also has a habit of stealing the names of other people!

** Since this was conveyed to me by another “Kennedy” student I can only treat this as hearsay at the time of this writing.

*** It is believed that “Kennedy” had gained foreknowledge of Shaffer’s chemistry and tasked Jack Pi to develop a competing route that could be patented.   As I have mentioned several times earlier in this blog series, Jack was one of the few skilled chemists in the “Kennedy” group at that time and he was the only one who was specifically trained in silicon chemistry.  It is unknown if U. Akron filed patent applications on the copycatted invention made by “Kennedy”.  The author of this blog estimates that U. Akron has spent > $1×106 on “Kennedy’s” patents!

**** The author of this blog has invented two of the ≈ 5-6 known (i.e., reported) Si based initiator systems.  Only one of these has the author of this blog reported which is patent pending and published.48,49


(1) Baird, M. C. Polymerization of iso-butylene. US Patent 5448001, 1995.

(2) Baird, M. C. Carbocationic Alkene Polymerizations Initiated by Organotransition Metal Complexes: An Alternative, Unusual Role for Soluble Ziegler-Natta Catalysts. Chem. Rev. 2000, 100,1471-1478.

(3) Barsan, F.; Karan, A. R.; Parent, M. A.; Baird, M. C. Polymerization of Isobutylene and the Copolymerization of Isobutylene and Isoprene Initiated by the Metallocene Derivative Cp*TiMe2(µ-Me)B(C6F5)3. Macromolecules 1998, 31,8439-8447.

(4) Bochmann, M.; Dawson, D. M. The Aluminocenium Cation [AI(C5H5)2]+: A Highly Effective Initiator for the Cationic Polymerization of Isobutene. Angew. Chem., Int. Ed. 1996, 35,2226-2228.

(5) Bochmann, M.; Garratt, S. Process for production of butyl rubber. US Patent 7041760, 2006.

(6) Bohnenpoll, M.; Ismeier, J.; Nuyken, O.; Vierle, M.; Schon, D. K.; Kuhn, F. Process for the production of highly reactive polyisobutenes. US Patent 7291758, 2007.

(7) Burns, C. T.; Shapiro, P. J.; Budzelaar, P. H. M.; Willett, R.; Vij, A. Bis(permethylcyclopentadienyl)aluminum Compounds: Precursors to [Cp*2Al]+ but Not to Cp*3Al. Organometallics 2000, 19,3361-3367.

(8) Carr, A. G.; Dawson, D. M.; Bochmann, M. Zirconocenes as Initiators for Carbocationic Isobutene Homo- and Copolymerizations. Macromolecules 1998, 31,2035-2040.

(9) Carr, A. G.; Dawson, D. M.; Bochmann, M. The [Zr(N{SiMe3}2)3]+cation as a novel initiator for carbocationic isobutene homo- and isobutene/isoprene co-polymerisations. Macromol. Rapid Commun. 1998, 19,205-207.

(10) Collins, S.; Piers, W. E.; Lewis, S. P. Polymerization of i-butane in hydrocarbon media using bis(borane) co-initiators. US Patent 7196149, 2007.

(11) Garratt, S.; Carr, A. G.; Langstein, G.; Bochmann, M. Isobutene Polymerization and Isobutene-Isoprene Copolymerization Catalyzed by Cationic Zirconocene Hydride Complexes. Macromolecules 2003, 36,4276-4287.

(12) Garratt, S.; Guerrero, A.; Hughes, D. L.; Bochmann, M. Arylzinc Complexes as New Initiator Systems for the Production of Isobutene Copolymers with High Isoprene Content. Angew. Chem., Int. Ed. 2004, 43,2166-2169.

(13) Hijazi, A. K.; Yeong, H. Y.; Zhang, Y.; Herdtweck, E.; Nuyken, O.; Kühn, F. E. Isobutene Polymerization Using [CuII(NCMe)6]2+ with Non-Coordinating Anions as Catalysts. Macromol. Rapid Commun. 2007, 28,670-675.

(14) Huber, M.; Kurek, A.; Krossing, I.; Mulhaupt, R.; Schnockel, H. [AlCp2]+: Structure, Properties and Isobutene Polymerization. Z. Anorg. Allg. Chem. 2009, 635,1787-1793.

(15) Jacob, S.; Pi, Z.; Kennedy, J. P. Cationic polymerizations at elevated temperatures by novel initiating systems having weakly coordinating counteranions 2. Isobutylene/isoprene copolymerizations. Polym. Bull. 1998, 41,503-510.

(16) Jacob, S.; Pi, Z.; Kennedy, J. P. Highest molecular weight polyisobutylenes and isobutylene copolymers by initiating systems having weakly coordinating counteranions. Polym. Mater. Sci. Eng. 1999, 80,495.

(17) Jianfang, C.; Lewis, S. P.; Kennedy, J. P.; Collins, S. Isobutene Polymerization Using Chelating Diboranes: Reactions of a Hindered Pyridine with Carbocations Bearing α-Protons. Macromolecules 2007, 40,7421-7424.

(18) Kennedy, J. P.; Collins, S.; Lewis, S. P. Polymerization of i-butene in hydrocarbon media using bis(borane) co-initiators. US Patent 7,202,317, 2007.

(19) Kostjuk, S. V.; Ganachaud, F. Cationic Polymerization of Styrene in Solution and Aqueous Suspension Using B(C6F5)3 as a Water-Tolerant Lewis Acid. Macromolecules 2006, 39,3110-3113.

(20) Kostjuk, S. V.; Ouardad, S.; Peruch, F.; Deffieux., A.; Absalon, C.; Puskas, J. E.; Ganachaud, F. Carbocationic Polymerization of Isoprene Co-initiated by B(C6F5)3: An Alternative Route toward Natural Rubber Polymer Analogues? Macromolecules 2011, 44,1372-1384.

(21) Kostjuk, S. V.; Radchenko, A. V.; Ganachaud, F. Controlled/Living Cationic Polymerization of p-Methoxystyrene in Solution and Aqueous Dispersion Using Tris(pentafluorophenyl)borane as a Lewis Acid: Acetonitrile Does the Job. Macromolecules 2007, 40,482-490.

(22) Kumar, K. R.; Hall, C.; Penciu, A.; Drewitt, M. J.; Mcinenly, P. J.; Baird, M. C. Isobutene Polymerization Initiated by [CP*TiMe2]+ in the Presence of a Series of Novel, Weakly Coordinating Counteranions. J. Polym. Sci., Part A: Polym. Chem. 2002, 40,3302-3311.

(23) Kumar, K. R.; Penciu, A.; Drewitt, M. J.; Baird, M. C. Isobutene–isoprene copolymerization initiated by [Cp*MMe2][(n-C18H37E)B(C6F5)3] (M=Ti, Hf; E=O, S) and related compounds. J. Organomet. Chem. 2004, 689,2900-2904.

(24) Langstein, G.; Bochmann, M.; Dawson, D. M. Process for the production of polyisoolefins by means of novel metallocene type initiator systems. US Patent 5703182, 1997.

(25) Langstein, G.; Bochmann, M.; Dawson, D. M.; Carr, A. G.; Commander, R. Controlled preparation of polyisoolefins at high temperatures using a new initiator system based on titanium, zirconium and hafnium cyclopentadienyl hydrides and a boron compound. DE Patent 19836663 A1, 2000.

(26) Lee, S.-J.; Shapiro, P. J.; Twamley, B. Synthesis and Characterization of [(C5Me4H)2Al]+, an Initiator for the Polymerization of Isobutene. X-ray Crystal Structures of [(C5Me4H)2Al(µ-Cl)]2 and [(C5Me4H)2Al][B(C6F5)4]. Organometallics 2006, 25,5582-5586.

(27) Lewis, S. P.Project 1. Synthesis of PIB-Silsesquioxane Stars via The Sol-Gel Process  Project 2. Solution and Aqueous Suspension/Emulsion Polymerization of Isobutylene Coinitiated by 1,2-C6F4[B(C6F5)2]2., Ph.D. Thesis, The Univ. of Akron, Diss. Abstr. Int. 2004, vol. 65, p. 770. Cf: Chem. Abs. 2004, vol. 143, p. 173195., 2004.

(28) Lewis, S. P. Heterogeneous Perfluoroaryl Substituted Lewis Acid Catalysts for Cationic Polymerizations. US Patent 8283427, 2012.

(29) Lewis, S. P.; Henderson, L.; Parvez, M. R.; Piers, W. E.; Collins, S. Aqueous Suspension Polymerization of Isobutene Initiated by 1,2-C6F4[B(C6F5)2]2. J. Am. Chem. Soc. 2005, 127,46-47.

(30) Lewis, S. P.; Jianfang, C.; Collins, S.; Sciarone, T. J. J.; Henderson, L. D.; Fan, C.; Parvez, M.; Piers, W. E. Isobutene Polymerization Using Chelating Diboranes: Polymerization in Aqueous Suspension and Hydrocarbon Solution. Organometallics 2009, 28,249-263.

(31) Lewis, S. P.; Piers, W. E.; Taylor, N.; Collins, S. Isobutene Polymerization Using a Chelating Diborane Co-Initiator. J. Am. Chem. Soc. 2003, 125,14686-14687.

(32) Li, Y.; Voon, L. T.; Yeong, H. Y.; Hijazi, A. K.; Radhakrishnan, N.; Köhler, K.; Voit, B.; Nuyken, O.; Kühn, F. E. Solvent-Ligated Copper(II) Complexes for the Homopolymerization of 2-Methylpropene. Chem. Eur. J. 2008, 14,7997-8003.

(33) Lin, M.; Baird, M. C. Benzyl group abstraction from Ti(CH2Ph)4 by B(C6F5)3 and [Ph3C][B(C6F5)4] to form Ziegler–Natta and carbocationic alkene polymerization initiators. J. Organomet. Chem. 2001, 619,62-73.

(34) Mathers, R. T.; Lewis, S. P. Aqueous Cationic Olefin Polymerization Using Tris(pentafluorophenyl)gallium and Aluminum. J. Polym. Sci., Part A. Polym. Chem. 2012, 50,1325-1332.

(35) Nuyken, O.; Vierle, M.; Kuhn, F. E.; Zhang, Y. Solvent-Ligated Transition Metal Complexes as Initiators for the Polymerization of Isobutene. Macromol. Symp. 2006, 236,69-77.

(36) Pi, Z.; Kennedy, J. P. Cationic Polymerizations at Elevated Temperatures by Novel Initiating Systems Having Weakly Coordinating Counteranions. 1. High Molecular Weight Polyisobutylenes, Nato Sci. Ser., Ser. E. ed.; In Ionic Polymerizations and Related Processes; Puskas, J. E., Ed.; Kluwer: Dordrecht, Neth., 1999; Vol. 359, pp 1-12.

(37) Radhakrishnan, N.; Hijazi, A. K.; Komber, H.; Voit, B.; Zschoche, S.; Kühn, F. E.; Nuyken, O.; Walter, M.; Hanefeld, P. Synthesis of Highly Reactive Polyisobutylenes Using Solvent-Ligated Manganese(II) Complexes as Catalysts. J. Polym. Sci., Part A 2007, 45,5636-5648.

(38) SaBmannshausen, J. Cationic and dicationic zirconocene compounds as initiators of carbocationic isobutene polymerization.   Dalton Trans. 2009, 9026-9032.

(39) Shaffer, T. D. Noncoordinating anions in carbocationic polymerization. Tris(pentafluorophenyl)boron as a Lewis acid catalyst.; In Cationic Polymerization; Faust, R., Shaffer, T. D., Eds.; American Chemical Society: Washington, D.C., 1997;  pp 96-105.

(40) Shaffer, T. D. Cationic Catalysts and processes for using said catalysts. US Patent 6699938, 2004.

(41) Shaffer, T. D.; Ashbaugh, J. R. Carbocationic Polymerization with Noncoordinating Boron Gegenions. Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem. 1996, 37,339-340.

(42) Shaffer, T. D.; Ashbaugh, J. R. Noncoordinating anions in carbocationic polymerization. J. Polym. Sci., Part A: Polym. Chem. 1997, 35,329.

(43) Shaffer, T. D.; Dias, A. J.; Finkelstein, I. D.; Kurtzman, M. B. Cationic Polymerization Catalysts. US Patent 6291389, 2001.

(44) Song, X.; Thornton-Pett, M.; Bochmann, M. Synthesis, Structure, and Reactivity of (C5H4SiMe3)2Y{(µ-FC6F4)(µ-Me)B(C6F5)2}: Tight Ion Pairing in a Cationic Lanthanide Complex. Organometallics 1998, 17,1004-1006.

(45) Tse, C. J. W.; Kumar, K. R.; Drewitt, M. J.; Baird, M. C. Isobutene polymerization and copolymerization with isoprene initiated by [Cp*TiMe2]+ in the presence of a novel type of weakly coordinating counteranion. Macromol. Chem. Phys. 2004, 205,1439-1444.

(46) Vierle, M.; Zhang, Y.; Herdtweck, E.; Bohnenpoll, M.; Nuyken, O.; Kuhn, F. E. Highly Reactive Polyisobutenes Prepared with Manganese(II) Complexes as Initiators. Angew. Chem., Int. Ed. 2003, 42,1307-1310.

(47) Nava, M.; Reed, C. A. Organometallics 2011, 30,4787-4800.

(48) Lewis, S. US Patent 2010/0273964, 2010.

(49) Liu, Q.; Mathers, R. T.; Damodaran, K.; Godugu, B.; Lewis, S. P. Greener, cleaner polymerization of isobutene. Green Materials 2013, 1,161-175.

2 thoughts on “University of Akron/Professor Joseph P. Kennedy Expose, Part 19

  1. I have a question. I’ve read your blog entries, and I am wondering what the end game is for you. If you find out what Kennedy’s real name is, what will you do next?

    • I will be commenting more in the future on the author of this comment. They have no less than seven different aliases. Should the reader be surprised they are connected to “Dr. Joseph P. Kennedy”??? As the saying goes, birds of a feather flock together…

Leave a Reply

Your email address will not be published.