Synthesis of Nickel based
Compounds for use as
Catalysts in
Polymerization Reactions
MATTHEW HURLOCK
Polymers

Polymer: a substance, that molecularly, is chiefly
made up of a large number of repeating units,
monomers, bonded together to form a larger
structure

Polymerization: a reaction that bonds monomer
units together to form a larger polymer chain

The high volume of uses today
Polymerization

Chain growth


Reaction of the functional groups of the
monomers
Step Growth

Free-Radical Growth

Coordination Polymerization
Catalysts

What is a Catalyst?

A substance that increases the rate of a
chemical reaction without itself undergoing any
permanent chemical change

Gives ability to control reactivity and synthesize
a variety of polymers

Why study Catalysts?

Control reactivity

Costs
Celluloid

First developed by Alexander Parkes and
made from Cellulose nitrate and Camphor

Hyatt brothers first to develop efficient
production method

Considered first Thermoplastic

Used for products such as:

Billiard Balls

Movie Film

Table Tennis Balls
Bakelite

Discoed by Leo Handrick Baekeland in 1907

Produced through Condensation of Phenol and
Formaldehyde

First fully synthetic polymer

Structure Highly irregular
Bakelite Products

Many uses

Telephones

Radios

Toys
Polyvinyl Chloride (PVC)

Discovered on accident by Eugen Bauman in 1872

Made commercially in 1926

Produced trough the Free-Radical polymerization of
Vinyl Chloride
Polyvinyl Chloride (PVC)

Major Polymer used today in products such as:

Piping

Vinyl records

Water resident fabrics

Credit/Debit cards
Polyethylene

Accidentally discovered by Fawcett and Gibson in
1931

Initially Produced using high-pressures synthesis

In the 50’s, discovery of two new synthetic pathways
to make polyethylene using metal catalysts

World’s Largest produced polymer
Polyethylene

Used for Plastic Bags, Piping, Medical products,
bubble wrap, milk jugs
Nylon

Nylon 66 first example of nylon to be developed in
1935 by W. H. Carothers and colleagues

Nylon 6 was developed after, as a means to get
around patents

Chain growth polymerization through condensation
reaction
Nylon

Products include: toothbrushes, stockings,
parachutes and flak vests
Polycarbonate

Discovered in 1898 by
Alfred Einhorn

In the 50’s Herman Schenell
filled the first patent for
polycarbonate

Produced through
Condensation
Polymerization
Polycarbonate

Products include: Electronic components, CDs and
DVDs, bullet resist glass, phones and safety glasses
Kevlar

Synthesized by Stephanie
Kwolek in the 60’s.

5 times the tensile strength
of steel

Produced through a
condensation
polymerization reaction

Applications: protective
clothing, ropes and cables,
smart phones, canoes, tires
Research

Objective: Synthesize nickel hydride compounds,
through the use of fluorinated ligand precursors, for
use as catalysts

Followed literature procedures that used nonfluorinated ligands

Started with the synthesis of a Ni precursor
compound with labile ligand

To determine if the a synthesis were successful
we used Nuclear Magnetic Resonance (NMR)
Reactions

Attempted Synthesis of (dfmp)4Ni
X

Synthesis of (dfepe)Ni(cod)
Synthesis of Ni(cdt)

Synthesis of Ni(cdt)

Next step similar to:
Reactions with Ni(cdt)
Synthesis of Ni(1,5-Hexadiene)2

Next step similar to:
Reactions with Ni(1,5-hexadiene)2
Conclusions

Attempted to synthesize Nickel hydride compounds
for use as catalyst in polymerization reactions

Why did the fluorinated ligands not bind to Nickel?


Electron poor quality of Phosphorous
Next step: look for more labile Nickel compound to
allow fluorinated ligands to bond
References

Bellis, M. The History of Plastics.
http://www.thebuttonmonger.com/content/The_History_of_Plastics.pdf (accessed April 2016).

Bonrath, W.; Pӧrshke, K. R. Angew. Chem. [Online] 1990, 102, 295.

Brydson, J. A. Plastic Materials.7th ed.; Butterworth-Heinemann: Oxford, 1999.

Chem1 Virtual Textbook: a Reference Text for General Chemistry, Polymers and Plastics and
introduction. http://www.chem1.com/acad/webtext/states/polymers.html#401 (accessed
April 2016).

Chemical Engineering Department: IIT Bombay, Mechanisms of Polymerization.
http://www.che.iitb.ac.in/faculty/sm/CL442/notes/POLYM-REACT.pdf (accessed April 2016).

Chemical Heritage Foundation, The History and Future of Plastics.
http://www.chemheritage.org/discover/online-resources/conflicts-in-chemistry/the-case-ofplastics/all-history-of-plastics.aspx (accessed April 2016).

Ogoshi, S.; Morita, M.; Inoue, K.; Kurosawa, H. J. Organomet. Chem. [Online] 2004, 689, 662665.

Polymer Expert, A History of Polymers. http://www.polymerexpert.fr/en/presentation/histoiredes-polymeres/ (accessed 2016).

Polymer Science Learning Center, Ziegler-Natta Vinyl Polymerization.
http://pslc.ws/macrog/ziegler.htm#pol (accessed April 2016).

Pӧrshke, K. R.; Pluta, C.; Proft, B.; Lutz, F. Zeitschrift für Naturforschung. [Online] 1993, 48, 608-626.
References

Wikipedia, Bakelite. https://en.wikipedia.org/wiki/Bakelite (accessed April 2016).

Wikipedia, Celluloid. https://en.wikipedia.org/wiki/Celluloid (accessed April 2016).

Wikipedia, Kevlar. https://en.wikipedia.org/wiki/Kevlar (accessed April 2016).

Wikipedia, Nylon. https://en.wikipedia.org/wiki/Nylon (accessed April 2016).

Wikipedia, Polycarbonate. https://en.wikipedia.org/wiki/Polycarbonate (accessed April 2016).

Wikipedia, Polyethylene. https://en.wikipedia.org/wiki/Polyethylene (accessed April 2016).

Wikipedia, Polystyrene. https://en.wikipedia.org/wiki/Polystyrene (accessed April 2016).

Wikipedia, Polytetrafluorethylene. https://en.wikipedia.org/wiki/Polytetrafluoroethylene
(accessed April 2016).

Wikipedia, Polyvinyl Chloride. https://en.wikipedia.org/wiki/Polyvinyl_chloride (accessed April
2016).

University of Purdue Chemistry department, Polymerization Reactions.
http://chemed.chem.purdue.edu/genchem/topicreview/bp/1polymer/reactions.html#free
(accessed April 2016).