1. Synthesis of Nickel based Compounds for use as Catalysts in Polymerization Reactions
Matthew Hurlock

2. 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
Polymer: a substance, that molecularly, is chiefly made up of a large number of repeating units bonded together to form a larger structure
Polymerization: reacting monomers together to form a polymer
Two forms of polymerization reactions chain growth: successive addition of monomers to the reactive end
Step growth is the reaction of functional groups of the monomer molecules.
Commercially useful because it turns abundant and more or less useless compounds into everyday products.
Products using polymers: PVC piping
Nylon fabrics
Nonstick Cookware
Kevlar vest

3. Polymerization Chain growth
Reaction of the functional groups of the monomers
Step Growth
Free-Radical Growth
Coordination Polymerization
Free-Radical: A free radical initiator is made which will then start the reaction process. Free radicals are highly reactive and will react readily with alkenes forming a new radical. This can then continue reacting to other alkenes. Termination of a chain occurs when two radical combine. Produces low density polymers
Coordination: This is an example of a Ziegler- Natta catalyst (TiCl4 mixed with Al(CH2CH3)2) need to remove oxygen and water due to reactivity with catalyst. Alkenes with donate electrons form the double bond to the Ti forming a bond. This will continue to occur thought the new alkenes will then form bonds between each other making a chain. This can produce very long straight chains which form high density polymers.
Should the next slide be polymers types or catalyst??

4. 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
What is a Catalyst?
A substance that increases the rate of a chemical reaction without itself undergoing any permanent chemical change
Less energy is required to make the reaction occur an thus the reaction is fast generally requires lower temperatures. Catalyst do this by providing an alternative, lower energy route, to the end point.
Catalysts can participate in multiple chemical transformation so generally a small amount is needed.
Why study?
To develop catalyst that can synthesis polymers with specific properties. And produce catalyst that do not react with certain compounds such as solvents.
Lower the cost, Ti is much more expensive than Ni due to relative abundance, cheaper catalyst mean cheaper polymer synthesis, therefore cheaper consumer products.

5. 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
Since its discovery in 1838 cellulose was one of the first know polymer chains with repeating units of glucose.
Alexzander Parke found that upon evaporation of solvent of photographic collodion produced a hard, horny as in the material that makes the horns of animals, elastic and waterproof substance. In 1856 he took out a patent for the waterproofing of fabrics through the use of such solutions.
In 1865, John Wesley Hyatt was trying to develop a new material for the production of billiard balls, at the time the were made out of ivory and the popularity and growth for the game was more than the ivory trade could keep up with. In 1870 J. W. Hyatt and his brother took out a patent for the production of a horn-like material through the use of cellulose nitrate( cellulose that has been treated with nitric acid) and camphor. ( Chemical Formula of C10H16O, a waxy solid that comes for the camphor laurel evergreen of Asia.) First time called celluloid.
Production: Taking Nitrocellulose and treating it w/ a solution of 50% camphor in alcohol. This changes the structure of the nitrocellulose to a gel of nitrocellulose and camphor. This is then pressed into blacks and then cab be fabricated into different uses.
Because of the Hyatt brothers Celluloid became the first exploited polymer plastic. And was used in a Varity of things from billiard balls to movie film to table tennis balls
Still in use today though on smaller scale.

6. Bakelite Discoed by Leo Handrick Baekeland in 1907
Produced through Condensation of Phenol and Formaldehyde
First fully synthetic polymer
Structure Highly irregular
Formaldehyde polymers had been know about since the second have of the 19th century and reaction involving formaldehyde and phenols to give resins had been conducted for much of the same amount of time
Leo Hendrik Baekeland was the first to discover a method to make a material that could be used to make useful products with. In 1907 he patented the method for the production of Bakelite.
Production: Formed from a condensation reaction of phenol with formaldehyde. . Heating of phenol and formaldehyde in presence of acid catalyst under pressure. Talk about catalyst??
Contains repeating units of Methyl Phenols, the structure thought is not strictly changes and can branch. (SHOW IMAGES)
Products: Due to its heat and scratch resistance and low conductivity bakelite was used in many products and use exploded during WWII
Used in : Electrical industry, telephones, piolet goggles, jewelry, instruments like sax, radios,
Easy to mold and cheap

7. Bakelite Products Many uses Telephones Radios Toys
Still used in some products today like such things as dominos, jewelry and dice

8. Polyvinyl Chloride (PVC)
Discovered on accident by Eugen Bauman in 1872
Made commercially in 1926
Produced trough the Free-Radical polymerization of Vinyl Chloride
Discovery: First discovered by Eugen Bauman in 1872 on accident through leaving an flask of vinyl chloride exposed to light. Polymerization synthesis of PVC patented in 1912 by Ivan Ostromislensky it wasn't used commercially until 1927 due to decomposition at production temps. Waldo Semon & Goodrich developed a method to make a more flexible and more easily processed material by blinding it with additives.
Production: Suspension polymerization: so a mixture of the monomers in liquid phase, in water, is radical polymerization VCM and water introduced into tank that is pressure tight and is constantly string. Initiators are added to start reaction. OVC is then cooled and dried to remove VCM and water then additives added.
Products: Piping (almost half of world production goes to piping), signs, vinyl records, water resistant fabrics

9. Polyvinyl Chloride (PVC)
Major Polymer used today in products such as:
Piping
Vinyl records
Water resident fabrics
Credit/Debit cards
Many inflatable things like mattress, beach balls and other such items.

10. 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
Discovery: In 1931 Fawcett and Gibson were conducting studies on effects of pressures to organic systems. Noticed that one of the ethylene tanks had lost pressure and a waxing substance had formed on the walls of the container. It was found to be a polymer of ethylene upon analysis. In 1935 Perrin developed a way to reproduce the accident using high pressure synthesis
Production: Until the 50’s polyethylene was synthesized through polymerization reactions at high pressures. The out come was highly branched polymers with moderate molecular weights. In 1954 two new routes were developed using metal catalysts, The Philips process and the Ziegler process. These processes could be done at lower temperatures and pressures and would give higher density, higher softening points and harder polymers
This is where catalyst really become big in the world of polymers. Many different types of catalysts have been made to make very specific forms of polyethylene. This is one of the reasons that polyethylene is so big in the world is because all of the different types can which include: high density, medium density, low density, ultra low density
Products: Grocery Bags, piping, medical products such as replacement hips, bubble wrap, milk jugs

11. Polyethylene
Used for Plastic Bags, Piping, Medical products, bubble wrap, milk jugs
Most common polymer used in commercial products.

12. Nylon
Nylon 66 first example of nylon to be developed in by W. H. Carothers and colleagues
Nylon 6 was developed after, as a means to get around patents
Chain growth polymerization through condensation reaction
Discovery: Name for a family of polymers, the first example was synthesized and discovered in 1935 by W. H. Carothers and is known as Nylon 66. German chemist developed nylon 6 as a means to get around patents for Nylon 66. The numbers indicate the amount of carbons in the raw materials used to form nylons.
Production: A condensation polymer and most are made through reacting dicarboxylic acid with a diamine. This polymerization is done through chain growth
Products: Tooth brushes, women’s stockings, parachutes and flak vests

13. Nylon
Products include: toothbrushes, stockings, parachutes and flak vests

14. Polycarbonate Discovered in 1898 by Alfred Einhorn
In the 50’s Herman Schenell filled the first patent for polycarbonate
Produced through Condensation Polymerization
Discovery: Discovered in 1898 by Alfred Einhorn but after 30 years the material was abandoned without commercialization. In 1953 Herman Schenell resumed the research and in 1955 filed a patented for the first linear polycarbonate.
Production:
Products: Electronic components, CDs and DVDs, bullet resist glass, phones and safety glasses

15. Polycarbonate
Products include: Electronic components, CDs and DVDs, bullet resist glass, phones and safety glasses

16. Kevlar Synthesized by Stephanie Kwolek in the 60’s.
Produced through a condensation polymerization reaction
5 times the tensile strength of steel
Applications: protective clothing, ropes and cables, smart phones, canoes, tires
Development: Synthesized by Stephanie Kwolek in the 60’s. Was going to be rejected but when tested the fiber did not break like nylon. Saw commercial production by the 70’s
Production: Synthesized form 1,4 –phenylene-diamine and terephthaloyl chloride in a condensation reaction. And results in a liquid crystalline behavior and is then spun to produce a fiber
Products: protective clothing, ropes and cables, smart phones, canoes, tires
Expensive
UV degradation

17. Research
Objective: Synthesize nickel hydride compounds, through the use of fluorinated ligand precursors, for use as catalysts
Followed literature procedures that used non- fluorinated 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)
List the rxns attempted using diagrams of rxns
let know why did or didn’t work and why we think that
Mention what the ultimate goal was, what we wanted to synthesize in the end.
Mention how we determine if rxns worked (NMR: how in depth should go? Using magnetic field the instrument can detect structural arrangements of the atoms within compounds) mention that how we would test catalytic ability (small scale polymerization rxns)

18. Reactions X Attempted Synthesis of (dfmp)4Ni
Synthesis of (dfepe)Ni(cod) X

19. Synthesis of Ni(cdt)
Synthesis of Ni(cdt)
Next step similar to:

20. Reactions with Ni(cdt)

21. Synthesis of Ni(1,5-Hexadiene)2
Next step similar to:

22. Reactions with Ni(1,5-hexadiene)2

23. 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
Summarize research: Knowledge of such catalyst is an integral part of the materials used today
Knowledge of such catalyst is an integral part of the materials used today
Ending statement along the lines of all of the advancements that continually change day to day life
Ending Statement: Knowledge of such catalyst is an integral part of the materials used today and have large affects on everyday life

24. References
Bellis, M. The History of Plastics. (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. (accessed April 2016).
Chemical Engineering Department: IIT Bombay, Mechanisms of Polymerization. (accessed April 2016).
Chemical Heritage Foundation, The History and Future of Plastics. plastics/all-history-of-plastics.aspx (accessed April 2016).
Ogoshi, S.; Morita, M.; Inoue, K.; Kurosawa, H. J. Organomet. Chem. [Online] 2004, 689,
Polymer Expert, A History of Polymers. des-polymeres/ (accessed 2016).
Polymer Science Learning Center, Ziegler-Natta Vinyl Polymerization. (accessed April 2016).
Pӧrshke, K. R.; Pluta, C.; Proft, B.; Lutz, F. Zeitschrift für Naturforschung. [Online] 1993, 48,

25. References
Wikipedia, Bakelite. (accessed April 2016).
Wikipedia, Celluloid. (accessed April 2016).
Wikipedia, Kevlar. (accessed April 2016).
Wikipedia, Nylon. (accessed April 2016).
Wikipedia, Polycarbonate. (accessed April 2016).
Wikipedia, Polyethylene. (accessed April 2016).
Wikipedia, Polystyrene. (accessed April 2016).
Wikipedia, Polytetrafluorethylene. (accessed April 2016).
Wikipedia, Polyvinyl Chloride. (accessed April 2016).
University of Purdue Chemistry department, Polymerization Reactions. (accessed April 2016).