Table Of ContentUniversity of Pennsylvania
ScholarlyCommons
Publicly Accessible Penn Dissertations
Winter 12-21-2011
Living Radical Polymerization Catalysts: Synthesis,
Application, and Utilization of Polymer Products in
the Synthesis of Metal Nanoparticles
Sara E. Hayik
University of Pennsylvania,
Living Radical Polymerization Catalysts: Synthesis, Application, and
Utilization of Polymer Products in the Synthesis of Metal Nanoparticles
Abstract
Living Radical Polymerization Catalysts: Synthesis, Application, and Utilization of Polymer Products in the
Synthesis of Metal Nanoparticles
Sara Elizabeth Hayik
Supervisor: Professor Bradford B. Wayland
Living radical polymerization techniques are powerful tools for prepared specialty polymer products used in
applications from biotechnology to electronics. Development of catalysts for the diferent methods is
important for increased versatility. Te goals of this research were to develop new radical addition-
fragmentation chain transfer (RFT) and cobalt mediated radical polymerization (CMRP) catalysts and
utilize polymers produced through controlled radical polymerization techniques for the synthesis of metal
nanoparticles. Vanadium complexes were designed to mimic conventional RFT chain transfer agents and
tested in the polymerization of methylacrylate (MA) and styrene. Tese complexes proved unsuitable for use
as RFT catalysts. Several cobalt complexes, using salen and salen derivative ligands, were prepared and tested
as CMRP catalysts for the polymerization of MA and vinyl acetate (VAc). (R,R)-N,N'-Bis(3,5-di-tert-
butylsalicylidene)-1,2-cyclohexanediamino Cobalt (II) proved to be the most promising candidate for both
polymers. MA was prepared with PDIs 1.32 and under while the VAc PDIs were under 1.50. In both cases,
observations suggesting a controlled polymerization were reported. PDMAEMA synthesized using a RFT
polymerization was used to stabilize and control the formation of platinum, gold, and palladium
nanoparticles. Protonation of the polymer chains using succinic acid or acidic metal complexes allowed for
ionic cross-linking by the metal anions, which is observed through DLS analysis. Reduction of the metal
complexes was then performed within the nanogel and the rapid stabilization by the polymer results in small
well defned particles. Well defned particles were produced for each metal with diferent size ranges for each.
Nanogel formation is critical mechanism for control in each system and was seen only in systems containing
dianionic species
Degree Type
Dissertation
Degree Name
Doctor of Philosophy (PhD)
Graduate Group
Chemistry
First Advisor
Dr Bradford B. Wayland
Tis dissertation is available at ScholarlyCommons: htp://repository.upenn.edu/edissertations/437
Keywords
living radical polymerization, metal nanoparticles, polymerization, nanogel, LRP catalysts
Subject Categories
Inorganic Chemistry
Tis dissertation is available at ScholarlyCommons: htp://repository.upenn.edu/edissertations/437
LIVING RADICAL POLYMERIZATION CATALYSTS: SYNTHESIS, APPLICATION, AND
UTILIZATION OF POLYMER PRODUCTS IN THE SYNTHESIS OF METAL NANOPARTICLES
Title Page
Sara Elizabeth Hayik
A DISSERTATION
In
Chemistry
Presented to the Faculties of the University of Pennsylvania
In
Partial Fulfillment of the Requirements for the
Degree of Doctor of Philosophy
2011
Supervisor of Dissertation
_____________________________
Bradford B. Wayland, Professor of Chemistry
Graduate Group Chairperson
_____________________________
Gary A. Molander, Professor of Chemistry
Dissertation Committee
Larry G. Sneddon, Professor of Chemistry
Christopher Murray, Professor of Chemistry
So-Jung Park, Assistant Professor of Chemistry
LIVING RADICAL POLYMERIZATION CATALYSTS: SYNTHESIS, APPLICATION, AND
UTILIZATION OF POLYMER PRODUCTS IN THE SYNTHESIS OF METAL NANOPARTICLES
COPYRIGHT
2011
Sara Elizabeth Hayik
Dedication
To my family and friends,
I would have never made it without you.
iii
Acknowledgements
First I would like to thank my dissertation advisor Dr. Bradford Wayland. Dr. Wayland
allowed me the freedom to grow as scientist, teacher and person. I am extremely grateful for his
guidance throughout my graduate experience and for the introduction to a field in which I had no
experience. Dr. Wayland provided me with the opportunity to find a path to teaching without
which I would never have found what I believe is my true calling.
I would also like to thank Dr. Mike Fryd who provided both personal and scientific support.
Mike introduced me to the world of nanotechnology and was always there to challenge my
assumptions. Mike’s optimism was always welcome in the face of unexpected results. This
characteristic has forever changed my scientific viewpoint leading me down the path of how and
why versus just looking at the whats.
I sincerely appreciate all of the time that my dissertation committee has given to my
endeavor. Dr. Larry Sneddon, Dr. So-jung Park, and Dr. Chris Murray have all provided me with
an excellent support system and have asked excellent and challenging questions. I would also
like to thank Dr. Michael Therien who served on my committee in the early stages of my work.
The support staff of the University of Pennsylvania Chemistry department is superb. I
would especially like to thank Bruce and Rico for always being there to fix the lab, move heavy
items, or just for a talk. Mandy Swope provided an incredible amount of guidance as I planned
these final few steps and without her I would have been helpless. Andre and Cong were always
there to brighten my day on trips to the stockroom and Tommy Nguyen kept all of my teaching
responsibilities in line.
Dr Susan Phillips provided me with incredible teaching freedom. I will forever be
extremely grateful for this opportunity. I entered graduate school terrified of teaching and left a
teacher. Sue’s incredible support and trust gave me this confidence and completely changed my
future.
I could not have asked for better classmates without whom I do not believe I could have
made it through the trials and tribulations of the last few years. Dr. Dan Himmelberger, Dr. Julie
iv
Aaron, Dr. Ian Farrell, Diana (Cabral) Challen provided me with some of my best times at Penn at
lunches, Dining Days, Livestrong, and the many wonderful celebrations including my wedding. Dr
Fernando Jove, Dr. Sounak Sarkar, and Dr Chi-How Peng were fantastic groupmates. I would
also like to thank the members of the Sneddon group especially Ariane Perez-Gavilin and Emily
Berkley, who provided me with both entertainment and help throughout my stay on the third floor.
Jen Scricco welcomed me into the group and guided me in the infancy of my research. I would
like to express my sincere gratitude to Amanda Kamps who performed the TEM imagining of my
nanoparticle without which my work would not have been complete. I would also like to thank
Amanda and Sean for all of the hours of nerd games. I would like to thank Dr. Andre Isaacs, Xi-
Jun Chen, Rob Hickey, Dierdre Sandrock, Ben Dyme, and Daniell Reifsnyder for their friendship.
The love of chemistry does not begin in college so I would like to thank Mrs Teri Miller for
introducing me to chemistry in high school. Mrs. Miller’s excitement and wonderful teaching gave
me the spark to further pursue the field. The opportunities I was given in high school were well
beyond the expected and for that I am extremely grateful. I am also so appreciative of her
patience since I know I was not always the best student.
Dr. Edward Rajaseelan took the spark and turned it into a flame during my time at
Millersville University. I have never met a teacher who is his equal and I can only hope to
someday be a fraction of what he was to me to my own students. Dr. R. saw in me what I did not
see in myself and for that I am forever grateful.
I would like to thank my family who have always supported me. My in-laws Joe and
Winnie have been supportive of both Seth and I throughout the graduate school process. A love
of science, exploration, and science were seeded early in me by my Grandma Nichols,
persistence seems to be a family trait handed down through my GrammyDoris, and all of my
grandparents have provided unwavering support of my somewhat untraditional path. My parents,
Sheila and Dave, may never have understood what I was doing scientifically but were always
there for me in the ups and downs of graduate school. My brothers, Keith and Jeremy, never let
v
me get a big head but were always there especially Keith who saved me from so very many car
disasters. Yes I am finally done with that paper everyone!
Finally I would like to thank Seth who has been the proofreader, the motivator, the
sounding board, and every other niche I have needed filled. I know I have not always made it
easy for him but I know I would have never made it this far without his patience, guidance, and
most of all his love. I will also always appreciate him letting us get our three cats who have been
ever so helpful writing my dissertation. Seth has always let me go with my crazy projects no
matter the inconvenience, including the huge piles of dissertation materials all over the house.
Seth and I have grown up as a couple together from awkward teenagers to what feels like an old
married couple. We have come so far and made it through so much and I cannot wait to see
what our future holds. Thank you, thank you, thank you!
vi
Abstract
LIVING RADICAL POLYMERIZATION CATALYSTS: SYNTHESIS, APPLICATION, AND
UTILIZATION OF POLYMER PRODUCTS IN THE SYNTHESIS OF METAL NANOPARTICLES
Sara Elizabeth Hayik
Supervisor: Professor Bradford B. Wayland
Living radical polymerization techniques are powerful tools for prepared specialty
polymer products used in applications from biotechnology to electronics. Development
of catalysts for the different methods is important for increased versatility. The goals of
this research were to develop new radical addition-fragmentation chain transfer (RAFT)
and cobalt mediated radical polymerization (CMRP) catalysts and utilize polymers
produced through controlled radical polymerization techniques for the synthesis of metal
nanoparticles. Vanadium complexes were designed to mimic conventional RAFT chain
transfer agents and tested in the polymerization of methylacrylate (MA) and
styrene. These complexes proved unsuitable for use as RAFT catalysts. Several cobalt
complexes, using salen and salen derivative ligands, were prepared and tested as
CMRP catalysts for the polymerization of MA and vinyl acetate (VAc). (R,R)-N,N'-
Bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediamino Cobalt (II) proved to be the
most promising candidate for both polymers. MA was prepared with PDIs 1.32 and
under while the VAc PDIs were under 1.50. In both cases, observations suggesting a
controlled polymerization were reported. PDMAEMA synthesized using a RAFT
polymerization was used to stabilize and control the formation of platinum, gold, and
palladium nanoparticles. Protonation of the polymer chains using succinic acid or acidic
metal complexes allowed for ionic cross-linking by the metal anions, which is observed
vii
