POLYMERIZATION AND PROPERTIES OF POLYTETRAFLUOROETHYLENE By Wes Overton

Molecular Visualization Using Methods of Computational Chemistry Mr. Lewis Acampora, Dr. Cheryl Dammann Summer Ventures in Science and Mathematics, 2001 UNC at Charlotte

POLYMERIZATION AND PROPERTIES OF POLYTETRAFLUOROETHYLENE

Abstract Polytetrafluoroethylene, better known as Teflon, is made up of a long string of tetrafluoroethylene monomers, or single molecules, each with two Carbon atoms and four terminal Fluorine atoms. To form the polymer, or fiber, Teflon, these monomers must undergo Free Radical Vinyl Polymerization, where they form bonds with other tetrafluoroethylene monomers. The energies of the polymerization were calculated for the polymerization of polytetrafluoroethylene, as well as polyethylene, a similar substance with four Hydrogen atoms in the terminal positions instead of the four Fluorine atoms. The data shows that the energy of polymerization for the tetrafluoroethylene were almost twice as much as the energies of polymerization for ethylene. Background Polytetrafluoroethylene is a long chain of tetrafluoroethylene monomers bonded together. The monomer tetrafluoroethylene is made up of two central carbon atoms that are double bonded together and have four Fluorines bonded in the terminal positions, as shown.
Fluorine Atoms Carbon Atoms

Tetrafluoroethylene Monomers

A portion of a PTFE Strand

Teflon was discovered by accident in a DuPont Chemical Company lab in the late 1930s. Dr. Roy J. Plunkett was researching chemical refrigerants and was preparing an experiment with polytetrafluoroethylene. When Plunkett attempted to pump the gaseous tetrafluoroethylene into Hydrochloric acid to initiate the experiment, he observed that nothing was coming out. He weighed the canister and it was still full. Plunkett then cut the cylinder open and discovered that the tetrafluoroethylene had polymerized and was a flaky white powder. After studying the powder, the DuPont scientists called it the most chemically inert substance they had ever seen (Discovery, 1998). Teflon is an extremely repellent substance that sticks to nothing (Polytetrafluoroethylene, 1996). This is because Fluorine atoms do not like to be around other elements when it is part of a molecule. Since polytetrafluoroethylene is made up of Fluorine atoms bonded to a Carbon backbone chain, they try to stay as far away from other molecules as possible. Fluorine atoms do, however, attract other Fluorine atoms, so chains of polytetrafluoroethylene are strongly attracted to each other (Polytetrafluoroethylene, 1996). Teflon, since it does not stick to anything, is widely used in commercial industry to make products such as non-stick cookware. It is also used to clean carpet and other fabrics, and it is even used to make artificial body parts, since the body rarely rejects it (Polytetrafluoroethylene, 1996). Polymerization In order for these monomers to become the polymer tetrafluoroethylene, or Teflon, they must go through a process called polymerization, where the bonds in the monomer are broken and the atoms re-bond to other tetrafluoroethylene molecules to form a long, selfperpetuating chain reaction. This happens in three steps: the initiation, propagation, and termination (Polymerization, 1998).

Initiation. Since tetrafluoroethylene contains a Carbon-Carbon double bond, it is considered a vinyl polymer. Thus, the monomer is polymerized through the free radical vinyl polymerization process to form the polymer polytetrafluoroethylene. The polymerization begins with one tetrafluoroethylene monomer, called the Initiator molecule, breaking apart. When this happens, two electrons are left unpaired, and they become the Initiator Fragments, also called Free Radicals. These Free Radicals easily pair up with one of the double bonded Carbons in tetrafluoroethylene, leaving the other to be the new Free Radical Initiator Fragment (Polymerization, 1998). Propagation. Propagation, the process of continually producing a Free Radical, allows tetrafluoroethylene to continue to be added to the chain reaction (Polymerization, 1998). Termination. There are two main kinds of termination reactions: Coupling and Disporportionation. In the coupling reaction, two unpaired electrons on the Carbon atoms bond to each other naturally, joining their chains of polytetrafluoroethylene as shown (Polymerization, 1998).

Singly Occupied Molecular Orbitals of ethylene as they begin Coupling.

Polyethylene molecule after completing the Coupling reaction. Bond formed by the coupling reaction.

In disporportionation, as two tetrafluoroethylene chains come close together, the unpaired electron of one of the Carbon atoms bonds with a Fluorine atom, instead of the other unpaired Carbon atom. Then the two unpaired electrons on the Carbon atoms on the other chain bond with each other, forming a Carbon-Carbon double bond, terminating the reaction.

The result of this polymerization is a polytetrafluoroethylene polymer (Polymerization, 1998).

Polytetrafluoroethylene polymer after polymerization.

The complete synthesis of polyterafluoroethylene takes place through the following steps (Polymerization, 1998):

CaF2 +H2SO4 -> CaSO4 + 2 HF CH4 +3 Cl2 -> CHCl3 +3 HCl CHCl3 +2 HF -> CHClF2 + 2 HCl 2 CHClF2 -> CF2CF2 + 2 HCl

Hydrogen Atoms

Methods All calculations were done using WaveFunctions PC Spartan Pro, a molecular visualization research program, version 1.0.5 in the Semi-Empirical method and PM3 level of calculation. As stated above, tetrafluoroethylene has four Fluorines bonded to the Carbons. A very similar structure to tetrafluoroethylene is ethylene, which has four Hydrogens bonded to the two Carbons, as shown above. The energies of ethylene and polyethylene were calculated and compared to those of tetrafluoroethylene and polytetrafluoroethylene to show the difference in energy in the Carbon-Hydrogen bonds and the Carbon-Fluorine bonds. First, a group of five ethylene monomers was made and the energy was calculated.

Ethylene monomers

The energy of an H2 molecule was then added to that value, since on the polyethylene there are two extra Hydrogens on the ends. A polyethylene molecule with ten Carbon atoms was then constructed and the energy was also calculated.
Polyethylene polymer

The energies of these two molecules were subtracted, and the energy difference was 130.8079381 kcal/mol. The same procedure was performed for the tetrafluoroethylene molecule.

Tetrafluoroethylene monomers

Comparison of Polymerization Energies in Ethylene and Tetrafluoroethylene

5 Ethylene Mon omer s 84.01 kcal/ mol Polyethylene Polyme r (10 Carbon s) -59.50 kcal/m ol H2 5 TFE Mon omer s -796.82 kcal/ mol PTFE Poly mer (10 Carb ons) -1061.54 kcal/ mol F2 Difference in Ethyl ene 130.81 kcal/ mol Difference in TFE

-12.70 kcal/ mol

-13.00 kcal/ mol

251.72 kcal/ mol

Results The energy of an F2 molecule was added to the energy of the tetrafluoroethylene monomer. When this value was subtracted from the value of the polytetrafluoroethylene polymer, the energy difference was 251.7229988 kcal/mol. This shows that the bond energy, or how strongly the electrons are attracted to the molecule, for the tetrafluoroethylene increased by almost twice as much as the ethylene did. In addition, polytetrafluoroethylene had a dipole moment of 0.421 debye, while polyethylene had a dipole moment of only 0.006 debye, showing that polytetrafluoroethylene is more polar than polyethylene. This is to be expected, since the Fluorine atoms distort the electron density of the Carbon backbone chain of polytetrafluoroethylene more than the Hydrogens distort the electron density in the backbone chain of polyethylene. Conclusion In conclusion, the bond strengths in the polytetrafluoroethylene were much stronger than those of the polyethylene. This shows that the polytetrafluoroethylene will be harder to break apart and form bonds with than the polyethylene. The reason that the bonds are stronger in the polytetrafluoroethylene is that the Fluorine atoms are very electronegative and do not like forming bonds with other atoms, except for other Fluorine atoms (Polytetrafluoroethylene, 1996).

REFERENCES

Discovery of Polytetrafluoroethylene. Retrieved July 11, 2001 from the World Wide Web: http://aml.airzona.edu/classes/mse222/1998/teflon/discovery.htm Free Radical Vinyl Polymerization of Polytetrafluoroethylene. Retrieved July 9, 2001, from the World Wide Web: http://aml.arizona.edu/classes/mse222/ 1998/teflon/polymerization.htm Polytetrafluoroethylene. Retrieved July 10, 2001, from the World Wide Web: http://www.psrc.usm.edu/macrog/ptfe.htm