Shortly after delivering my formal talk, scientists from Firestone who had been in attendance approached “Dr. Kennedy” and informed him that the basic chemistry I was working on had recently been patented by Kaneka (see JP 11209702, JP 11209701, WO 19990225, and so on).  Immediately “Kennedy” turned on me stating “It is your fault, it was your responsibility.”  At that time I was surprised by the dramatic change in “Kennedy’s” demeanor.  For many months I received nothing but praise and was told to focus on conducting actual research work.  At that time I had continued to do generalized (keyword) searches on SciFinder Scholar^®; however, none of them produced any hits.  Likewise, “Kennedy” had conducted numerous searches with the assistance of the head science librarian at the time, Ann Bolek, and still nothing relating to the project had been uncovered.  This unusual twist of fate was the first indication to me that “Kennedy” was not a man of his word as he had reneged on his promise to “protect my soft underbelly.”

In response to the finding that much of the chemistry had more or less be patented, focus was shifted to increasing the silica content of the star core through the use of alkoxy silanes (and even titanium alkoxides for hybrid structures) but the primary thrust of my work was temporarily shifted by “Kennedy.”  “Kennedy” informed me that Firestone was going to pay his research group money (according to him, part of which would fund me) and in return I was to teach one of their scientists (Terry Hogan) how to conduct living polymerization of IB.  Starting several days following the visit by Firestone scientists I began to generate new project ideas (see below) that would be related to the work I had been conducting so that I could tie the two together and finish the requirements necessary for my Ph.D. without losing much if any time.  From this point forward Dr. “Kennedy” offered no useful ideas in regards to work I was involved in.  It was in June of 2000 when I officially began a series of interactions with Dr. Hogan at U. Akron and taught him the basic aspects of living polymerization of IB while at the time I continued to work on the PIB silsesquioxane star project.  Dr. Hogan then was able to reduce to practice an invention that he had made involving copolymerization of styrenic monomers bearing reactive siloxy groups with IB to make a moisture curable form of PIB (see US 6838539).  Hogan’s invention was patented and Dr. “Kennedy” somehow got his name listed as a coinventor, despite the fact that Hogan told me personally that “Kennedy” made no inventive contributions whatsoever.  Interestingly, no money through Firestone ever came my way despite Hogan informing me that Firestone had paid “Kennedy” approximately $2,000.  At this point I was beginning to slowly realize what Dr. “Kennedy” was really about when it came to polymer science.

Despite these revelations I continued to work in the area of PIB-silsesquioxanes and transitioned into some of the chemistry I had proposed to “Kennedy” concerning the use of polyhedral oligomeric silsesquioxanes (POSS).  Unbeknownst to me several more twists of fate were about to transpire…

Lewis Ideas 1 Lewis Ideas 2 Lewis Ideas 3 Lewis Ideas 4

With the assistance of Jack and practice I was soon making silyl functionalized PIBs necessary for the research project.  With the exception of holidays or when he was out on travel I submitted monthly reports to Dr. “Kennedy” (see examples below).  As the project progressed I slowly became aware of the fact that Dr. “Kennedy” had very little insightful input to give in regards to problems that I was experiencing in the condensation of these arms into stars.  Another thing that I continued to encounter were issues related to equipment failures, mostly in the dry box that I used but also in instrumentation (e.g. GPC and NMR).  At times progress was hampered by the fact that I was becoming routinely ill with severe difficulty in breathing, something that was abnormal for me.  Regardless of the setbacks, I was able to figure out alternative methods (e.g. nonhydrolytic sol-gel synthesis) that led to improved yields of star polymers and within approximately one year following the beginning of laboratory work I had amassed enough data to deliver my formal talk as required by the polymer science department (see below).

Shortly after this talk (4-15-00) a physician informed me that my health problems were due to severe asthma and it was speculated that a major factor in causing this (which I did not have prior) could have been due to exposure to volatile reagents in the “Kennedy” lab.  Unfortunately, while at U. Akron I never once received any formal safety training and had been exposed to some unsafe practices in the handling of solvents commonly used in the “Kennedy” lab.  From that point forward I began to incrementally implement safer handling procedures when it came to use of reagents; however, I had already suffered the physical damage that they could cause.  Sadly this was but one bit of bad news to occur during this period as the reader will see…

Report Si 4_4_99  Report Si 6_4_99  Report Si 7_8_99  Report Si 8_18_99                Report Si Nov_99  Report Si Dec_99  Report Si 2_5_00

Formal abstract

formal talk

My first (and only mentor at U. Akron) was Zhengjie (aka Jack) Pi.  Jack originated from Claire Tessier’s research group in the adjacent chemistry department at U. Akron.  His background was as an organometallic chemist who specialized in silicon chemistry.  Unbeknownst to me at the time was the fact that Dr. “Kennedy” knew very little about silicon chemistry and that Jack was highly instrumental in helping “Kennedy” catch up to the curve of front running scientists in the field of isobutene (IB) polymerization by mimicking work from a well-known industrial chemist (i.e. Dr. Tim Shaffer).  The reader will soon see that this is a repetitive pattern when it comes to Dr. “Kennedy” and that in many instances patents, research work, and principles described in some of his books are essentially direct copies of other researchers.

During the time I spent with Jack I learned the basics of the living polymerization of IB and very rudimentary air-sensitive manipulations.  I use the adjective “rudimentary” as “Kennedy’s” lab did not contain modern day dry boxes nor did it have anything that could be remotely described as a fully functioning Schlenk line.  Likewise, the techniques I learned were in fact substandard and not what could be termed stringent in terms of such manipulations.  At the time my ignorance of such chemistry prevented me from seeing the obvious fact that besides Jack no one else in the “Kennedy” research group was properly schooled in air-sensitive chemistry.  Despite these limitations, Jack was highly instrumental in getting me versed in the chemistry required to complete the research project assigned to me by Dr. “Kennedy.”  Within a relatively short period of time I was not only able to synthesize the required starting polymer (allylic functionalized PIB) but I was also able to convert it to ~100% silyl functionalized PIB, which was the precursor for the PIB silsesquioxane stars.  During this period Dr. “Kennedy” would routinely comment “just keeping doing lab work, I’ll worry about the literature” and also indicated his pleasure with the progress being made.  Despite his assurances, I continued to do my best in reviewing the scientific literature in context to the ongoing project; however, as the reader will see this was still not enough to prevent a crisis.