How Plastics Work

BY CRAIG FREUDENRICH, PH.D.

Chips from plastic soft drink and mineral

water bottle tops at the end of the recycling
process at the Aviv recycling plant in
Israel. See more pictures of green living.

Plastics are everywhere. While you're

reading this article, there are probably
numerous plastic items within your reach
(your computer, your pen, your phone). A
plastic is any material that can be shaped
or molded into any form -- some are
naturally occurring, but most are man-
made.

Plastics are made from oil. Oil is a carbon-

rich raw material, and plastics are large
carbon-containing compounds. They're large molecules called polymers, which are composed of
repeating units of shorter carbon-containing compounds called monomers. Chemists combine
various types of monomers in many different arrangements to make an almost infinite variety of
plastics with different chemical properties. Most plastic is chemically inert and will not react chemically
with other substances -- you can store alcohol, soap, water, acid or gasoline in a plastic container
without dissolving the container itself. Plastic can be molded into an almost infinite variety of shapes,
so you can find it in toys, cups, bottles, utensils, wiring, cars, even in bubble gum. Plastics have
revolutionized the world.

Because plastic doesn't react chemically with most other substances, it doesn't decay. Therefore,
plastic disposal poses a difficult and significant environmental problem. Plastic hangs around in the
environment for centuries, so recycling is the best method of disposal. However, new technologies
are being developed to make plastic from biological substances like corn oil. These types of plastics
would be biodegradable and better for the environment.

In this article, we'll examine the chemistry of plastic, how it's made, how it's used, and how it's
disposed of and recycled. We'll also look at some new biologically based plastics and their role in the
future of plastic.
Plastics History
A Bakelite telephone in "100 Years of Plastic"
at the Science Museum in London in 2007.
The exhibition was a celebration of plastics
timed to coincide with the 100th anniversary
of Leo Baekeland's invention of Bakelite.

Before the invention of plastic, the only

substances that could be molded were
clays (pottery) and glass. Hardened
clay and glass were used for storage,
but they were heavy and brittle. Some
natural substances, like tree gums and
rubber, were sticky and moldable.
Rubber wasn't very useful for storage
because it eventually lost its ability to
bounce back into shape and became sticky when heated.

In 1839, Charles Goodyear accidentally discovered a process in which sulfur reacted with
crude rubber when heated and then cooled. The rubber became resilient upon cooling -- it
could stretch, but it snapped back to its original shape. It also retained its resilience when
heated. We now know that the sulfur forms chemical bonds between adjacent rubber polymer
strands. The bonds cross-link the polymer strands, allowing them to "snap back" when
stretched. Charles Goodyear had discovered the process now known as vulcanization,
which made rubber more durable.

In 1846, Charles Schonbein, a Swiss chemist, accidentally discovered another polymer when
he spilled a nitric acid-sulfuric acid mixture on some cotton. A chemical reaction occurred in
which the hydroxyl groups of the cellulose fibers in the cotton were converted to nitrate
groups catalyzed by the sulfur. The resultant polymer, nitrocellulose, could burst into a
smokeless flame and was used by the military in place of gunpowder. In 1870, chemist John
Hyatt reacted nitrocellulose with camphor to make celluloid, a plastic polymer that was used
in photographic film, billiard balls, dental plates and Ping-Pong balls.

In 1909, a chemist named Leo Baekeland synthesized Bakelite, the first truly synthetic
polymer, from a mixture of phenol and formaldehyde. The condensation reaction between
these monomers allows the formaldehyde to bind the phenol rings into rigid three-dimensional
polymers. So, Bakelite can be molded when hot and solidified into a hard plastic that can be
used for handles, phones, auto parts, furniture and even jewelry. Bakelite is hard, resistant to
heat and electricity, and can't be easily melted or scorched once cooled. The invention of
Bakelite led to a whole class of plastics with similar properties, known as phenolic resins.
In the 1930s, a Dupont chemist named Wallace Carruthers invented a plastic polymer made
from the condensation of adipic acid and a certain type of diaminohexane monomers that
could be drawn out into strong fibers, like silk. This plastic became known as nylon. Nylon is
lightweight, strong and durable and became the basis of many types of clothing, coverings
(tents), luggage, bags and ropes.
The use of these early polymers became widespread following World War II and continues
today. They lead to the creation of many other plastics, like Dacron, Styrofoam, polystyrene,
polyethylene and vinyl.

PLASTICS PRIMER
We'll learn about all of these points in more depth later on, but for now, here are a few useful
tidbits about the structure of plastics.

 Plastics are polymers, large molecules made of repeating units of smaller molecules
(monomers) that are chemically bound together. A polymer is like a chain in which
each link is a monomer.
 All plastic is made of carbon. Man-made plastic uses carbon derived from oil, while
biopolymers or bioplastics use carbon derived from natural materials.
 There are a few ways that monomers combine to form the polymers of plastics. One is
a condensation reaction, where two molecules combine and a smaller molecule --
usually water, an alcohol or an acid -- is lost.

Chemistry of Plastics

All plastics are polymers, but not all polymers are plastics. Some familiar nonplastic polymers
include starches (polymers of sugars), proteins (polymers of amino acids) and DNA (polymers
of nucleotides -- see How DNA Works). The simplified diagram below shows the relationship
between monomers and polymers. Identical monomers can combine with each other to
form homopolymers, which can be straight or branched chains. Different monomers may
combine together to form copolymers, which also may be branched or straight.
The chemical properties of a polymer depend on:
 The type of monomer or monomers that make up the polymer. The chemical
properties of homopolymer 1 are different from those of homopolymer 2 or the
copolymers.
 The arrangement of monomers within the polymer. The chemical properties of the
straight polymers are different from those of the branched polymers.

The monomers that are found in many plastics include organic compounds like ethylene,
propylene, styrene, phenol, formaldehyde, ethylene glycol, vinyl chloride and acetonitrile (we'll
examine many of these as we discuss various plastics). Because there are so many different
monomers that can combine in many different ways, we can make many kinds of plastics.

Condensation and Addition Reactions

There are a few ways that monomers combine to form the polymers of plastics. One method
is a type of chemical reaction called a condensation reaction. In a condensation reaction,
two molecules combine with the loss of a smaller molecule, usually water, an alcohol or an
acid. To understand condensation reactions, let's look at another hypothetical polymer
reaction.

Monomers 1 and 2 both have hydrogen (H) and hydroxyl groups (OH) attached to them.
When they come together with an appropriate catalyst (an atom or a molecule that speeds up
the chemical reaction without being used up in it), one monomer loses a hydrogen while the
other loses a hydroxyl group. The hydrogen and hydroxyl groups combine to form water
(H2O), and the remaining electrons form a covalent chemical bond between the monomers.
The resulting compound is the basic subunit of copolymers 1 and 2. This reaction occurs over
and over again until you get a long chain of copolymers 1 and 2.

Another way that monomers can combine to form polymers is through addition reactions.
Addition reactions involve rearranging electrons of the double bonds within a monomer to
form single bonds with other molecules. Imagine that two people (each a monomer) stand
close together and each person has his/her arms folded (double bond). Then they unfold their
arms and hold hands (single bond). The two people now make a polymer, and the process
can be repeated.

Various polymer chains can interact and cross-link by forming strong or weak bonds between
monomers on different polymer chains. This interaction between polymer chains contributes
to the properties of specific plastics (soft/hard, stretchy/rigid, clear/opaque, chemically inert).
Now we'll learn about the different types of plastic.

Types of Plastics
Styrofoam cups are great insulators for hot liquids.

Plastics can be divided into two major categories:

1. Thermoset or thermosetting plastics. Once cooled and
hardened, these plastics retain their shapes and cannot return to
their original form. They are hard and durable. Thermosets can be
used for auto parts, aircraft parts and tires. Examples include
polyurethanes, polyesters, epoxy resins and phenolic resins.

2. Thermoplastics. Less rigid than thermosets, thermoplastics

can soften upon heating and return to their original form. They are
easily molded and extruded into films, fibers and packaging.
Examples include polyethylene (PE), polypropylene (PP) and polyvinyl chloride (PVC).
Let's look at some common plastics.

Polyethylene terephthalate (PET or PETE): John Rex Whinfield invented a new polymer in
1941 when he condensed ethylene glycol with terephthalic acid. The condensate was
polyethylene terephthalate (PET or PETE). PET is a thermoplastic that can be drawn into
fibers (like Dacron) and films (like Mylar). It's the main plastic in ziplock food storage bags.

Polystyrene (Styrofoam): Polystyrene is formed by styrene molecules. The double bond

between the CH2 and CH parts of the molecule rearranges to form a bond with adjacent
styrene molecules, thereby producing polystyrene. It can form a hard impact-resistant plastic
for furniture, cabinets (for computer monitors and TVs), glasses and utensils. When
polystyrene is heated and air blown through the mixture, it forms Styrofoam. Styrofoam is
lightweight, moldable and an excellent insulator.

Polyvinyl Chloride (PVC): PVC is a thermoplastic that is formed when vinyl chloride
(CH2=CH-Cl) polymerizes. When made, it's brittle, so manufacturers add a plasticizer liquid to
make it soft and moldable. PVC is commonly used for pipes and plumbing because it's
durable, can't be corroded and is cheaper than metal pipes. Over long periods of time,
however, the plasticizer may leach out of it, rendering it brittle and breakable.

Polytetrafluoroethylene (Teflon): Teflon was made in 1938 by DuPont. It's created by

polymerization of tetrafluoroethylene molecules (CF2=CF2). The polymer is stable, heat-
resistant, strong, resistant to many chemicals and has a nearly frictionless surface. Teflon is
used in plumbing tape, cookware, tubing, waterproof coatings, films and bearings.

Polyvinylidine Chloride (Saran): Dow makes Saran resins, which are synthesized by
polymerization of vinylidine chloride molecules (CH2=CCl2). The polymer can be drawn into
films and wraps that are impermeable to food odors. Saran wrap is a popular plastic for
packaging foods.

Polyethylene, LDPE and HDPE: The most common polymer in plastics is polyethylene,
which is made from ethylene monomers (CH2=CH2). The first polyethylene was made in
1934. Today, we call it low-density polyethylene (LDPE) because it will float in a mixture
of alcohol and water. In LDPE, the polymer strands are entangled and loosely organized, so
it's soft and flexible. It was first used to insulate electrical wires, but today it's used in films,
wraps, bottles, disposable gloves and garbage bags.

In the 1950s, Karl Ziegler polymerized ethylene in the presence of various metals. The
resulting polyethylene polymer was composed of mostly linear polymers. This linear form
produced tighter, denser, more organized structures and is now called high-density
polyethylene (HDPE). HDPE is a harder plastic with a higher melting point than LDPE, and it
sinks in an alcohol-water mixture. HDPE was first introduced in the hula hoop, but today it's
mostly used in containers.

Polypropylene (PP): In 1953, Karl Ziegler and Giulio Natta, working independently, prepared
polypropylene from propylene monomers (CH2=CHCH3) and received the Nobel Prize in
Chemistry in 1963. The various forms of polypropylene have different melting points and
hardnesses. Polypropylene is used in car trim, battery cases, bottles, tubes, filaments and
bags.

Making Plastics
Man-made plastics like these are derived from oil.

To make plastics, chemists and chemical engineers must do the

following on an industrial scale:
1. Prepare raw materials and monomers
2. Carry out polymerization reactions
3. Process the polymers into final polymer resins
4. Produce finished products

First, they must start with various raw materials that make up the
monomers. Ethylene and propylene, for example, come from
crude oil, which contains the hydrocarbons that make up the
monomers. The hydrocarbon raw materials are obtained from the "cracking process" used in
refining oil and natural gas (see How Oil Refining Works). Once various hydrocarbons are
obtained from cracking, they are chemically processed to make hydrocarbon monomers and
other carbon monomers (like styrene, vinyl chloride, acrylonitrile) used in plastics.

Next, the monomers carry out polymerization reactions in large polymerization plants. The
reactions produce polymer resins, which are collected and further processed. Processing can
include the addition of plasticizers, dyes and flame-retardant chemicals. The final polymer
resins are usually in the forms of pellets or beads.

Finally, the polymer resins are processed into final plastic products. Generally, they are
heated, molded and allowed to cool. There are several processes involved in this stage,
depending upon the type of product.

Extrusion: Pellets are heated and mechanically mixed in a long chamber, forced through a
small opening and cooled with air or water. This method is used to make plastic films.

Injection molding: The resin pellets are heated and mechanically mixed in a chamber and
then forced under high pressure into a cooled mold. This process is used for containers like
butter and yogurt tubs. (Custompart.net has a great lesson on injection molding.)

Blow molding: This technique is used in conjunction with extrusion or injection molding. The
resin pellets are heated and compressed into a liquid tube, like toothpaste. The resin goes
into the chilled mold, and compressed air gets blown into the resin tube. The air expands the
resin against the walls of the mold. This process is used to make plastic bottles.

Rotational molding: The resin pellets are heated and cooled in a mold that can be rotated in
three dimensions. The rotation evenly distributes the plastic along the walls of the mold. This
technique is used to make large, hollow plastic items (toys, furniture, sporting equipment,
septic tanks, garbage cans and kayaks).

Biopolymers and Recycling

Pioneer electronics researcher Tasuo Hosoda
displays a prototype model of a Blu-ray disc
made of corn starch polymer. On the right are
corn starch polymer pellets.

As we mentioned earlier, there are

other polymers besides plastics.
Naturally occurring polymers, such as
starches, cellulose, soy protein,
vegetable oil, triglycerides and bacterial
polyesters, can be extracted from crops
and bacteria. Furthermore, plants and
microorganisms can produce
substances like lactic acid, which can
be polymerized
into bioplastics (polylactic acid, for example). There are two strategies for producing
bioplastics.

Fermentation: Bacteria or other microorganisms mass-produce the biopolymers in

bioreactors (fermentation tanks). The biopolymers (lactic acid, polyesters) are extracted from
the bioreactors and chemically processed into plastics.

Genetic engineering plants as bioreactors: Biotechnologists introduce bacterial genes into

plants. These genes code for the enzymes to make bacterial plastics. The plants are grown
and harvested, and the plastics are extracted from the plant material.

In 1997, Cargille Dow made a clear plastic (polylactide) from corn. The polylactide fibers were
woven into sports apparel, upholstery fabrics and bioplastic wraps.

Bioplastics have the advantage of being produced from renewable resources (bacteria,
plants) rather than nonrenewable resources (oil, natural gas). Furthermore, bioplastics are
biodegradable -- they can break down in the environment (see How Landfills Work).
Bioplastics is a potentially important industry. With current technology, bioplastics might be
more expensive to produce, but biotechnology is rapidly advancing and production may
become more economical in the future.

Recycling Plastics
Oil-based plastics don't degrade, but many types (including PP, LDPE, HDPE, PET, and
PVC) can be recycled. Each type has a code and identifying number, but some plastics aren't
as economically feasible to recycle. So it's important to check with your recycler or
municipality about which types of plastics will be accepted.
Once collected, plastics go through the following steps
 Inspection to weed out contaminants and inappropriate types of plastic
 Shredding and washing
 Separation based on density
 Drying
 Melting
 Draining through fine screens to remove more contaminants
 Cooling and shredding into pellets
 Selling back to plastic companies

The discovery of plastics revolutionized our society by introducing a huge variety of

lightweight, strong, flexible products with many uses. Although plastics do pose disposal
problems, recycling is always a possibility. Furthermore, new research into biopolymers may
produce new bioplastic products from renewable resources that are biodegradable and easier
on our environment.