Being one of only two Americans in the “Kennedy” group was in some regards a positive experience for me. It was here that my interest in India and China grew and when Stas arrived a similar desire to learn about Russia emerged. In fact, my curiosity in these countries is still quite keen these days. So, for the first couple months I intently learned as much as I could from Stas in both the area of chemistry as well as Russia. Stas (please refer to files below this paragraph) had been polymerizing IB in eutectic mixtures containing primarily CaCl2, sometimes in the presence of a surfactant, and always using the Lewis acid ytterbium(III) trifluoromethanesulfonate {Yb(OTf)3}. This was a slight departure from the system that emerged from the Sawamoto group as no purposefully added initiator was present in Stas’ system and therefore the common consensus was that water was functioning in this role. Stas also demonstrated through the use of 1H NMR and modeling with triflic acid that two different types of PIBs were being formed in these polymerizations. One type of PIBs had low MWs and according to Stas’ modeling experiments (see files below this paragraph) these were formed by triflic acid impurities present in the Yb(OTf)3. The second type of PIBs possessed higher MWs and these were being formed by Yb(OTf)3, supposedly in conjunction with water (again, refer to files below this paragraph). IMA experiments by Stas also supposedly showed that these polymerizations possessed living characteristics to them (see files below this paragraph).
Early report by Stas (This report was presented by Stas during the first meeting with Dr. “Kennedy” and Dr. Lewis. The handwriting on the left is Stas’ the handwriting on the right is Dr. Lewis’.)
Early Stas IMA data set (This is a copy of data that Stas had generated. The handwriting is Dr. Lewis’.)
Stas 1st ima experiment (Another data set generated by Stas presented during one of the first meetings with Dr. “Kennedy” and Dr. Lewis.)
Another Stas ima experiment (This is yet another data set presented by Stas during a group meeting.)
1H NMR by Stas showing low and high MW PIBS (These are 1H NMR spectra generated by Stas that supposedly showed two types of propagating species. One being initiated by triflic acid the other being initiated by water in conjunction with Yb(OTf)3. Most of the writing is Stas’.)
Second meeting with Kennedy and Stas (These are notes taken by Dr. Lewis from the second meeting with “Kennedy” and Stas.)
Third meeting with Kennedy and Stas (These are notes taken during a third meeting by Dr. “Kennedy” who then passed them to Dr. Lewis.)
The experiments that I conducted with Stas (please see files below this paragraph) were not overly demanding when it came to manipulations; however, most were quite lengthy (many requiring 8 or more hours). Still, with Stas’ assistance, PIB was being made in aqueous media and “Kennedy” was happy. Oddly enough, “Kennedy” assigned other side projects. One involved the polymerization of IB by triflic acid followed by quenching with an amine in order to generate amine functionalized PIBs. The other involved the attempted polymerization of IB in aqueous media using BF3·OEt2 (which is again a basic polymerization system reported earlier by Sawamoto’s group). In all instances, with the exception of BF3·OEt2 polymerizations, experimentation was initially conducted with Stas (see below this paragraph for scanned copies of my notebook and of reports to “Kennedy” during this period).
Lab notebook Yb(OTf)3 scandal 1 (First section of lab notebook on Yb(OTf)3 project.)
Lab notebook Yb(OTf)3 scandal 2 (Second section of lab notebook on Yb(OTf)3 project.)
Lab notebook Yb(OTf)3 scandal 3 (Third section of lab notebook on Yb(OTf)3 project.)
Progress Report 12-13-00 (This was a report written primarily by Dr. Lewis covering details of work on the Yb(OTf)3 project much being done in conjunction with Stas. The corrections on this report were made by Dr. “Kennedy.”)
Progress report late dec into early jan (This was a report written primarily by Dr. Lewis covering details of work on the Yb(OTf)3 project much being done in conjunction with Stas.)
Progress report 1-13 to 26-00 (This was a report written primarily by Dr. Lewis covering details of work on the Yb(OTf)3 project much being done in conjunction with Stas. The corrections on this report were made by Dr. “Kennedy.”)
table amine functionality (This was a report written primarily by Dr. Lewis covering details of work on the triflic acid/amine functionalization project much being done in conjunction with Stas).
As time slowly passed on I began to venture out on my own in order to increase productivity and to hasten the time needed for graduation. Then I hit a brick wall. Every time I conducted experimentation on my own with the Yb(OTf)3 system I was unable to produce more than a few milligrams of product (if any) and in most instances those few milligrams of material were most likely surfactant (please see files below this paragraph). Stas and “Kennedy” informed me that my technique was to blame and so I returned to working with Stas in order to remedy this. Oddly enough, with his assistance we continued to make PIB but whenever I tried similar experiments on my own I was unable to generate polymer. I slowly began to question the previous results and increasingly began pointing out that polymer was only being generated when Stas was involved in experimentation (again, see files below this paragraph). As I did this, my relationship with both Stas and “Kennedy” progressively went downhill.
early April ca 9th 2001 progress report (Another report generated by Dr. Lewis where he begins to question the validity of the data being generated by Stas.)
Summary of Experimental Data 4-9-01 (Another report generated by Dr. Lewis where he begins to question the validity of the data being generated by Stas.)