Before I resume my previous blog I need to make a backwards digression.  Prior to making my discovery that Holy Grail was stable to hydrolytic cleavage in excess methanol (see below) and thus readily coming to the conclusion that polymerization of IB might be feasible in the presence of water (also see below)* a former research mate from “Kennedy’s” group paid me a visit.  At this moment I won’t disclose his name; however, I will say that he (like the vast majority of people who have emerged from this research group) is a coward.  This individual (as did everyone in the “Kennedy” group and many outside students too) knew quite well that I was being shafted for no good reason and yet not a single one of these people ever bothered to report anything to the department head or president of the university.  So when this person came to visit me in a distraught state because “Kennedy” had screwed him out of royalties stemming from this student’s invention I had little pity for him.  A picture of “Kennedy” receiving a royalty check for an invention made by this student is given below (and yes, I am invoking “fair use” in that this blog expose is in part for “educational” purposes, and for the general knowledge of the public as it no doubt exposes criminal activities {it will not come down without a large counter-lawsuit and even more public exposure}).  This picture shows George Newkome (current polymer science department head the last time I checked) along with Luis Proenza (current president of U. Akron), the latter is handing “Kennedy” the royalty check for the invention made by the student.

NMR exp that shows HG stable in MeOH, notebook 2 (this notebook page records Dr. Lewis’ discovery that Holy Grail was stable to hydroxylic cleavage)

First pzn exp IB aqueous media notebook 2 (These are the first notebook pages that record Dr. Lewis’ invention on aqueous polymerization of IB.  Much more will be said concerning this and related documents pertaining to this invention in subsequent blog postings.)

Dr. “Kennedy” receiving royalty check for a student’s invention

Furthermore, I wish to add that the witness to this invention can vouch with 100 % certainty that the aforementioned student was solely responsible not only for conception of the invention, but also for its reduction to practice and additionally made arrangements for the licensee to travel to U. Akron to negotiate patent licensing!  How can I make this statement?  I am the witness who signed the laboratory notebooks of this student recording his invention and additionally I also know the basic gist of how the invention came about.  All I will say is that in “Kennedy’s” lab no one (with the exception of Dr. Jack Pi) was well-versed with silicon chemistry and much of what the remainder knew was derived from the Gelest chemical catalog!  This was in part where this student gathered the necessary information needed to devise this invention (along with careful observations of what water does when present in a hydrosilation reaction mixture containing “Karstedt’s” catalyst).

As we will see in later blog postings, this habit of “Kennedy” in stealing inventions from others is not limited to this one student.  Moreover, as I will be pointing out in future blogs the chemical literature (both patent and peer reviewed articles) is replete with examples of patents that were issued to “Kennedy” (both while at Esso Corp. and U. Akron) which contain “prior art” content and thus never qualified as being “patentable” and definitely are unoriginal.  Some of the earliest articles and patents coauthored by “Kennedy” make false claims as to the originality of the research (e.g. polymerization using alkyl Al coinitiators or copolymers of IB with β-pinene) and can be readily traced as originating from peer scientists within the polymer community at the time in question or well prior to it…

* In later blog postings I will be providing numerous additional pieces of evidence that demonstrate conclusively that indeed I am the sole inventor of the first (and actually next two) aqueous polymerization systems for IB (i.e. the only aqueous polymerization systems for this monomer).  The second of these was reported by myself and a colleague a little over one year ago and the third will be reported sometime this year.

Note to reader:  Much of the information here is contained in my dissertation, copies of which can be found at both the science library as well as polymer science department at U. Akron.

I spent the remainder of my academic career working in the Collins’ lab.*  It was here that I actually learned the majority of my laboratory skills.  Most of these skills were not imparted by the teachings of people in this lab but instead were self-taught by reading texts such as “The Manipulation of Air-Sensitive Compounds” followed with repeated trial and error attempts to replicate what I had read.  Once I entered this research group the first task at hand was to synthesis a compound that was nicknamed “holy grail.”  This material was a perfluoroarylated chelating (i.e. bidentate) borane that has the formula 1,2-C₆F₄[B(C₆F₅)₂]₂ and it proved at that time to be very difficult to make (taking the better portion of one year).  During this period I made some minor improvements to the synthesis of this compound.  Several things stood out in stark contrast to my experience in “Kennedy’s” lab.

1. Collins’ equipment was modern (please see pictures below, which only show a portion of modern pieces of equipment).
2. Scott was well-versed in the types of manipulations that needed to be conducted and was excellent at deciphering NMR spectra.
3. Scott was a stickler for only publishing chemistry that was replicable and I can’t ever imagine him attempting to fabricate anything.
4. Dr. Collins also was a slave driver, and in that regard I learned to develop an even better work-ethic than I had before.

Grubb’s Still for purification of solvents.

IB being collected in a graduated tube on a specialized Schlenk line.

BBr3 being purified.

Next, I began exploration of the polymerization of IB under anhydrous conditions using “holy grail” as many analogous monodentate perfluoroarylated Lewis acids had been previously used in a similar manner.  It was not uncommon for me to spend 10-12 hour days, every day of the week working in an attempt to get my degree.  In addition to the synthesis of “holy grail” and the numerous other compounds had to be made (e.g. initiators, surfactants, etc.) just for polymerization studies, a large amount of time was devoted towards conducting modeling experiments.  During my stint in this lab I collected in excess of 1,000 NMR spectra (see picture below) and many experiments were quite time consuming (ca. 6-8 hours) where manual probe tuning between ¹H and ¹⁹F nuclei had to be conducted (in addition to manual shimming) over a temperature range of -80 to 25 °C.  Although keeping up the pace I had set was difficult, for the first time at U. Akron I was making good progress towards finishing a degree.  One other thing which made this period enjoyable was that I had no further contact with “Kennedy.”

Binders of GPC data and NMR spectra collected in Collins’ lab by Dr. Lewis.

During the latter part of modeling work, in an attempt to figure out why cumyl methyl ether was not an efficient initiator with “holy grail”, I made an important discovery.  The NMR spectra afforded on reaction of cumyl methyl ether seemed to indicate an unusual decomposition reaction and in order to shed light on its mechanism the a related reaction (that of methanol with “holy grail”) was explored.  All of the modeling experiments were very difficult as moisture had to essentially non-existent. They also had to be initially conducted at low temperatures (ca. -80 °C) and were further complicated by the fact that milligram or sub-milligram quantities of reagents were always involved.  Since money was very tight and the solvent of choice (CD₂Cl₂) was expensive the use of stock solutions (which would have facilitated proper stoichiometry) was out of the question.  After numerous attempts to add exceedingly tiny amounts of methanol (in a controlled manner) to an NMR tube I (out of desperation) added in a huge excess.  I was just sick and tired of banging my head up against the wall spending up to 8 hours at a time trying to get the proper conditions that would placate Collins.  This act of defiance was fortuitous as something very unusual occurred.  When the amount of methanol was close to that of “holy grail” decomposition always resulted but this time when methanol was in a huge excess no decomposition happened.  I was amazed that hydrolytic cleavage of “holy grail” did not occur and seeing that the pKa of methanol is close to water I formulated what would be my very first invention, aqueous polymerization of IB.

*The end result of all my work prior to graduation was no less than 3 notebooks full of data (for Collins alone), >> 1,000 NMR spectra, and several journal articles and patents (not to mention a 300 page dissertation).

At this point in time I thought it worthwhile to post a number of photographs taken at The University of Akron that provide additional credence to this blog series.  They say a picture is worth a thousand words, in this case “words of damnation” no doubt…

The following are pictures of “Kennedy’s” state of the art dry boxes and laboratory.  It should be obvious to the reader that this is a poor joke at being anything remotely up to date or for that matter in proper operating condition.

“Kennedy” Lab 1

“Kennedy” Dry Box 1

“Kennedy” Dry Box 2

“Kennedy” Dry Box 3

“Kennedy” Dry Box 4

“Kennedy” Dry Box 5

The following are pictures of “Kennedy’s” chemical storage.  Corrosion, leaking containers, etc. were commonplace as was improper mingling of reagents and storage methods.  Much of this mess was cleaned up prior to my departure from U. Akron by an unknown individual who appeared to show up (either retired or fired from) a local company (which the author believes was Firestone).  I’m guessing that individual had no life to speak of.

“Kennedy” Chem Storage 1

“Kennedy” Chem Storage 2

“Kennedy” Chem Storage 3

“Kennedy” Chem Storage 4

“Kennedy” Chem Storage 5

“Kennedy” Chem Storage 6

“Kennedy” Chem Storage 7

“Kennedy” Chem Storage 8

“Kennedy” Chem Storage 9

The polymer science department at U. Akron.  This is a good place to have one’s mental and physical health assaulted and ideas stolen all at the same time.

Polymer Science Bldg