Post on 25-May-2018
Dr. John J. Eisch Distinguished Professor, Organic Chemistry
Chemical and Personal Rearrangements
at the occasion of his Retirement Symposium October 28-29, 2011
In honor of
By Csaba A. Kovacs
10-28-2011
B.D.E. (Before Dr. Eisch)
1956-1957 For summers technician for Professor Bryce Maxwell
Princeton University’s Polymer Laboratory
1958 Thiokol
1960-1966 US Army’s Chemical Unit
1961-1966 Research Laboratories of the National Drug Company
1963-1966 Graduate Student with Professor Robert Koob, MS program
A.D.E. (After Dr. Eisch)
1966-1970 Graduate Student with Dr. John J. Eisch, Ph. D. Program
1970-1972 Research Fellow for Dr. John J. Eisch
1972-1974 Research Fellow at Wright Patterson Air Force Base
Polymer Laboratories
1974-1999 Senior Staff of Eastman Kodak’s Research Laboratories
2005-2010 Research Director of the Tianjin Zhaoyang Nanotechnology
Company’s Research and Development Laboratories
10-28-2011
B.D.E. (Before Dr. Eisch)
1956-1957 Summers technician for Professor Bryce Maxwell
Princeton University’s Polymer Laboratory Professor Maxwell was the inventor of the mechanical spectrometer to test
polymers for the loss modulus. Karl Rehn prepared poly propylene for the first time in March 1954. I was testing it in 1956. Polypropylene is in now a 65 billion/year commercial product.
1958, Thiokol Poly Urethane Foams
1960-66 US Army’s Chemical Unit Smoke Generator Operator
One 50 gallon drum of fog oil can cover 60 square miles (97 km) of land in 15 minutes.
1961- 66 Research Laboratories of the National Drug Company Pharmaceutical Chemist
In the 60-s, there was no modeling software to design active compounds. The shotgun approach
was used. A basic new core structure was selected or designed and different known active
groups were attached to it. (This always involved an extensive synthetic effort.) Then the
compounds were screened for biological activity.
1963-66 St Joseph University’s MS program with Dr. Robert Koob,
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1.75 2.27 3.93
Solvent Dipole Moment Effect on the o/p Ratio in the
Fries Rearrangement
Solvents:
o-Dichlorobenzene
Chlorobenzene
Nitrobenzene
Dipole Moment
O/P
Ratio
10-28-2011
The Start of my A.D.E. Period at
The Catholic University of America
One of Professor Eisch’s interest was to study the mechanism of
1,2 Anionic Rearrangements
10-28-2011
Found:
2-Pyridyl >Phenyl >4-Pyridyl
Migration Tendency
1,2 Rearrangement in the Reaction of Lithium with
2,2-Di phenyl-2-(2 or 4-pyridyl)ethyl Chloride
- Anticipated:
2-Pyridyl >4-Pyridy l>Phenyl CH3I
10-28-2011
Wright-Patterson Air Force Base –
Materials Laboratory
Polymer Division
My original research proposal was to prepare spiro-silane polymers.
For polymer formation very efficient reactions were needed.(> 90%)
A large number of reactions were investigated. Two are illustrated below.
1.
2.
Boeing B-52 Stratofortress
10-28-2011
Inter Layer Development for Polycarbonate and Glass
Requirements: 1. Good optical properties. 90% transmittance, <1% haze, U.V. stability, refractive index close to glass.
2. Good adhesion to glass and polycarbonate
3. High tensile and tear strength
4. Retain physical and mechanical properties at high temperature
(350-450º F)
Modification of Polymers
ACS Symposium Series
121, 31, p457-468
10-28-2011
Eastman Kodak Company
1974-1999
1. Sensitizing Dye
2. Photographic Chemistry
3. Mass Memory (Optical Disks)
4. Inkjet
Research Laboratories
My first assignment at Eastman Kodak Company was to
determine the reason for an imaging dye fade on long term
storage in in a product. The dye of interest was a carbocyanine
dye with a structure shown below.
US Patent 3,619,194
10-28-2011
Dye Decomposition Product
Solvent, 80ºC
Exposed Silver Salt + Developer Oxidized Developer
Oxidized Developer + Coupler Dye
Dye Formation in Color Photography
10-28-2011
Dye Based 14 inch Optical Disk
The Recording Layer
IR dye (λmax = 780nm)
with a mixture of inert
organic molecules forming
an amorphous glass on the
disk with spin coating.
10-28-2011
The Recording Layer
IR dye (λmax = 780nm) mixture forming an
amorphous glass on the disk using spin
coating.
Writable CD
10-28-2011
The Inkjet years.
Designing Ink Jet Inks is a Hard Process Things that have to be considered and controlled :
Print Quality, Print Speed, Reliability, Media Flexibility, Durability, Cost and Safety.
In order to be able to get excellent prints, all parts of the system have to work together.
These are: the printer, the driver,the ink, and the receiver.
Material Selection Ink Properties Jetability Ink Media Interactions
Ink Base
water
wax
polymer
monomer
solvent
resin
Colorant
dyes
pigments
Dispersants
Humectants
Penetrants
Surfactant
Biocide
Plasticizer
Buffer
Anti-foamer
Anti-bleeding agent
Anti-cockle agent
Chelating agent
Toxicity
Chemical Hazard
Fire Hazard
Dye solubility
Pigment content
Particle size
Stability
Color
Purity all materials
Viscosity
Surface tension
pH
Melting point
Specific heat
Specific gravity
Conductivity
Sound velocity
Bubble nucleation
Kogation
Crusting properties
Drop formation
Drop volume
Drop shape
Drop velocity
Drop frequency
Drop placement
Drop satellites
Nozzle clogging
Due to:
ink drying
contamination
Ink-Print head
compatibility:
Corrosion
precipitation
softening
swelling
Air bubble
Nozzle wetting
Nozzle crusting
Color quality
Dot size
Dot shape
Optical density
Banding
Dry time
Gloss uniformity
Feathering
Spreading
Bleeding
Coalescence
Water fastness
Smear fastness
Rub resistance
Scuff resistance
Fold resistance
Light and dark fastness
Curl
Cockle
10-28-2011
•Synonym: Astra Blue Base 6 GLL, Basic Blue 140
•Empirical Formula: C47H52CuN14O6S3
•Molecular Weight: 1068.75
•CAS Number: 82864-57-1
Stable Dye Based Inks
10-28-2011
Eastman Kodak Employment Chart in Rochester
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Employees
10-28-2011
What are Kodak’s problems?
Poor market intelligence
Limited understanding of the digital world
Comparing everything to film
No holding power
R&D Organization
Dr. Csaba A. Kovacs
Director & Chief Scientist
Product R&D Dept. Dr. Csaba A. Kovacs
Department Head
Analytical & System
Evaluation Dept. Dr. Csaba A. Kovacs
Department Head
Ink Technology Dev. Lab.
Wang, Wenjie
Lab Manager
Nanoparticle
Dispersion Lab.
for Ink
Shi,
Jinyong
Group Leader
Zhang,
Junling
Technologist
Wang,
Liyuan
Technician
Bio-
Nanoparticle
Dispersion
Lab.
Liu,
Xiaojie
Group Leader
Wang,
Nan
Technologist
Piezo Group
Liu,
Xiaobo
Group Leader
Deng,
Yingchun
Technician
Thermal Group
Du,
Wenfei
Group Leader
Chen,
Yang
Technologist
Advanced
Analytical Lab.
Vacant
Lab Manager
Zhong.
Liurong
Technician
Zhang,
Zhifang
Technician
Competitive
Analysis &
Control
Testing Group
Kang,
Suxia
Engineer
Northern
Light
Liu,
Xiaojie
Project
Manager
Special
Projects
Wen,
Pei
Engineer
Printing
System
Liu,
Hongfang
Engineer
New Technology &
Applications Group Dr. Csaba A. Kovacs
Chief Scientist
Tianjin Zhaoyang Nanotechnology Company
10-28-2011
Professor Eisch’s had a major influence on my life. His drive to develop an understanding for the nature of things and to have fun doing it was infectious.
It was a joy to bring an interesting observation or a new idea to Dr. Eisch. His brain started to race and hundreds of other ideas related to the problem popped into his head. He always respectfully listened to your ideas and logically evaluated them. I had many discussions with Professor Eisch mainly in front of the lab’s blackboard.
I never enjoyed chemistry as much as during my time with Dr. Eisch. The academic freedom, the ability to do new things and get exited about discoveries was never greater then during this period of my life. I still remember this time as the most fun part of my life.
For this I thank Professor Eisch profoundly.
10-28-2011