Taylor K.

Adkins
CBE 505
4/22/2022
Polytetrafluoroethylene
Polytetrafluoroethylene (PTFE), better known as Teflon, is an important industrial
chemical that has had a widespread set of applications, including everything from carpeting to
electronics to the coating on nonstick pans. More recently, PFTE has been utilized in engineering
materials, automotive and aeronautic industries, coatings, lubrications, and more. PFTE has many
relatively distinctive properties that make it especially well-suited to these varied purposes. It is
chemically inert, a useful property that allows it to circumvent the ravages of corrosion and has an
extremely low coefficient of friction, giving it the nonstick ability appreciated by many amateur
chefs everywhere. Additionally, PFTE has excellent thermal stability—having both an extremely
high melting point and good low-temperature performance. Polytetrafluoroethylene, as the name
suggests, is a fluoropolymer: a polymer containing fluorine in its structure. In fact, PFTE is what
is known as a perfluoropolymer; all the hydrogens in the analogous hydrocarbon structure are
replaced by fluorine atoms. This chemical swap is what leads to the relative inertness of PFTE
over its hydrocarbon cousin, polyethylene (PE). The carbon-fluorine bond is generally much
stronger than other carbon-halogen bonds and is in fact known as the strongest bond in organic
chemistry, leading to the characteristic inertness and stability. PFTE is widely considered the first
in an ever-growing collection of fluoropolymers—those polymers containing fluorine in their
chemical structures—a class of materials with many industrial applications, stemming from
fluorine’s characteristic stability, inertness, and bond strength with carbon.
The birth of PTFE is generally accepted to be during 1938 in the lab of Dr. Roy Plunkett
of DuPont. While trying to produce a new refrigerant, Plunkett planned to combine
tetrafluoroethylene (TFE) with HCl. Thus, he synthesized a large amount of TFE, a gas, in order
to have it at the ready for his future experiments. He attempted to store the gas for later use, but
unwittingly allowed the TFE to polymerize to PFTE. The polymer product was studied, and the
inertness and slickness were discovered, as well as its electrical insulating ability. Initially, DuPont
put it to use as an inert tank liner for the containers that stored materials for atomic bombs during
World War II. Few other materials were as successful resisting the corrosive power of uranium
hexafluoride. From there, the applications branched out to include machine coatings, cookware,
carpeting and more.
From its first conception, PTFE was expensive to produce and had a number of toxic
intermediates and byproducts. The first major synthesis method employed industrially was to
produce TFE from fluorspar (CaF2), sulfuric acid (H2SO4), and chloroform (CHCl3). The reaction
of fluorspar and sulfuric acid yields hydrofluoric acid (HF). This is reacted with the chloroform to
give monochlorodifluoromethane (CHClF2) and hydrochloric acid (HCl). The CHClF2 reacts with
itself to finally give the TFE as well as more HCl by-product. This method of production is known
as the pyrolysis of CHClF2. It is undesirable for a number of reasons, including the production of
byproducts like HF, HCl, and other undesirable perfluorocarbons that must be removed by
cryogenic scrubbing. However, the process is economically preferred for industrial applications,
due to the easy scale-up ability and optimization of HCl and HF recycling allow the process to run
cleanly. Currently, the process generally takes place in a reactor heated between 590°C-950°C.
The final product is distilled to remove impurities.
Other methods for producing TFE are only commonly practiced in the lab at this point.
They include the dehalogenation of halofluorocarbons, and the pyrolysis of perfluopropanoic acid
salts. CF2Cl- CF2Cl or CF2Br- CF2Br is reacted in a batch process with zinc as a catalyst to remove
the halogens. The reaction has good yield, but the starting materials are not readily available as
they have the potential to be ozone depleting. Pyrolysis of acid salts produces CO2 along with the
TFE, so it is not too commonly deployed, as polymer-grade TFE must be exceptionally pure, and
the salts must be obtained or synthesized. Neither of these methods have much promise to be
scaled-up as the current pyrolysis method employed in the industry performs the best financially.
The TFE gas will spontaneously polymerize, especially under pressure. It may also
decompose into carbon and CF4, so it is difficult to transport. This decomposition is exothermic
and in general TFE must be handled with extreme care due to its many safety risks. TFE is a
category 1 flammable gas and a category 1 carcinogenic. Thus, storage and safe handling is also a
difficulty. For these reasons, the industrial production of PFTE usually begins with synthesizing
TFE on site, instead of obtaining the TFE from a separate industrial producer.
There are a couple of main methods to conduct the polymerization reaction of TFE to PFTE
that lead to polymers of slightly different forms that are suitable for specific purposes. However,
virtually all TFE polymerization takes place as a batch or semi batch process, with semi batch
being most common; TFE is fed continuously to a reaction chamber pre-filled with material, and
the chamber is drained upon reaction completion. It is possible to run the process continuously;
however, semi-batch is the process practiced most in industrial settings.
The first major way to produce PFTE from TFE is via suspension polymerization. In
suspension polymerization, TFE enters a reaction chamber filled with water and an initiator,
commonly H2O2 or other organic peroxides. The reaction-chamber mixture can also contain other
chemicals, such as surfactants, anticoagulants, and pH buffers. The reaction begins as soon as the
TFE contacts the initiator. The whole reaction chamber is shaken such that the reaction will
progress more effectively better. The free-radical mechanism by which TFE polymerizes to PTFE
is exothermic, so the reaction chamber must be chilled by a cooling jacket. After the appropriate
extent of reaction is reached for the optimal degree of polymerization, the flow of TFE to the
reactor is stopped and the water/initiator mix is drained away as well, leaving the precipitated
PFTE, in the form of a stringy mass. The PFTE is dried and milled then formed into an
agglomerated pellet form that can be molded for different uses.
The other major way to produce PFTE is through dispersion or emulsion polymerization.
Again, this method employs a water/initiator/additives mixture to which TFE is introduced. The
mixture is gently agitated, but not roughly shaken, as in the suspension method, and a cooling
jacket is still employed. The PFTE forms into small beads, as opposed to the stringy mass obtained
in the suspension method. The water is mostly removed, leaving behind a white substance, known
as dispersion. The PFTE dispersion can be used as a liquid or dried as a powder after washing.
Any wastewater produced in the washing process must be treated as the perfluorinated byproducts,
dispersants, and surfactants contained in the wastewater can be potentially toxic.
Depending on the way that PFTE is polymerized, either dispersion or emulsion, the
properties of the final product can be a little bit different. Firstly, as with all polymers, the
molecular weight of the polymer can vary, and that affects the physical and mechanical properties.
Specifically, the crystallinity will be high for lower molecular weight products that were cooled
slowly and vice versa. The other property that impacts properties is the particle size. Particle size
of the final product has a significant impact on the future processing of the PFTE, with smaller
sized particles having higher tensile strengths and better resistance to flexing. Dispersion typically
is the method that produces smaller, bead-like particle size, and its products typically go into
applications like coatings. Suspension polymerization, on the other hand, produces more rod-like
particles and is used in different applications, like manufacture of electrical parts.
One potential area for research in terms of PFTE production is looking at using
supercritical CO2 as a solvent either purely or in conjunction with an aqueous medium in order to
improve the safety of the handling of TFE. A paper published in 1995 by a group at the University
of North Carolina at Chapel Hill shows that the morphology of the PFTE produced by conventional
dispersion polymerization method is comparable to that of the PFTE produced via the CO2/water
hybrid medium. TFE stabilizes greatly when stored with CO2 compared to storing pure TFE. Thus,
using CO2 as a medium for the polymerization would improve the safety as well as maintaining
the efficacy. However, as of yet, the technology is not practical for industrial applications, and
probably will not be developed for such as it is not hugely impactful on the final product.
PTFE manufacture, though, has a somewhat dark history. The community around a DuPont
facility manufacturing PFTE in West Virginia was suffering from various cancers and diseases.
After hearing from a farmer about cows dying inexplicably, attorney Robert Bilott discovered that
a surfactant that DuPont used in its production of Teflon was being dumped and infiltrating the
ground water in the community. The levels of the surfactant, perfluorooctanoic acid (commonly
referred to as PFOA or C8), were found to be more than DuPont’s own recommendations for
acceptable safety limits. The controversy is the topic of a documentary as well as a legal thriller
film Dark Waters that aired in 2019. Since 2015, using PFOAs has been banned and researchers
are interested in looking at more benign surfactants, both to people and the environment.
PFTE is an important industrial chemical with applications in electronics, construction,
chemical, and automotive industries due to its unique properties of having an extremely low
coefficient of static friction, incredible chemical inertness, low dielectric constant, and great
thermal stability. The monomer of TFE is typically produced from the pyrolysis of hydrofluoric
acid and chloroform. TFE is then industrially polymerized to PFTE by either suspension or
dispersion methods, though using CO2 as a solvent is being explored. The production of PFTE is
a little controversial, as in the recent past, surfactants used in the manufacturing process have been
found to cause various ailments, including cancer. Overall, PFTE has revolutionized aspects of
modern living, by providing the valuable services that only it, with its special blend of valuable
properties, can deliver, as well as birthing the industry of fluoropolymers, which is now a varied
and booming class of materials.

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