Plastic Polymers

By: Mrs. Ruth T. Libag, MA Chem, RMT, RPT

What are plastics?

Plastics are materials which can

be molded into different shapes
e.g. fibers, sheets, films, blocks, etc.
with or without the applications of
heat.
 Facts about plastics
Plastic needs about 450 years
just to start decomposing.
Then, it takes another 50-80
years to decompose
completely.
Facts about plastics

90% of the price you pay for

the bottled water goes to the
plastic bottle, while the water
cost you only 10% of the
money you give.
Facts about plastics

Sad but true, the worldwide

fishing industry throws huge
amounts of plastic garbage in
the oceans. Amazing 150,000
tons go into the water every
year, including packaging,
plastic nets, lines and buoys.
Facts about plastics

This trash causes death of

many animals in the seas,
which mistake the garbage for
food. Estimations say that the
number of killed animals is
over one million.
Distinguishing Polymers

PETE /PET- Polyethylene

terephthalate
HDPE- High density
polyethylene
V/ PVC- Polyvinyl chloride
LDPE- Low density
polyethylene
PP- Polypropylene
PS- Polystyrene
 PETE /PET- Polyethylene terephthalate

 Bottles for soft drinks, water,

sports drinks and containers for
condiments like ketchup, salad
dressing, etc.
 PET is considered safe, but it
can actually leach the toxic
metal antimony, which is used
during its manufacture.
 HDPE- High density polyethylene

 HDPE, which is considered a

low-hazard plastic, is often
used for milk, water and juice
bottles, as well as bottles for
cleaning supplies and
shampoo, grocery bags.
 HDPE (like most plastics) has
been found to release
estrogenic chemicals.
 V/ PVC- Polyvinyl chloride

 PVC plastic can be rigid or

flexible, and is commonly found in
bags for bedding, shrink wrap,
deli and meat wrap, plastic toys,
table cloths and blister packs
used to store medications. PVC
contains toxic chemicals
including DEHP, a type of
phthalate used as a plastics
softener. Phthalates are one of
the groups of "gender-bending"
chemicals causing males of many
species to become more female.
These chemicals have disrupted
the endocrine systems of wildlife,
causing testicular cancer, genital
deformations, low sperm counts
and infertility in a number of
species, including polar bears,
deer, whales and otters, just to
name a few.
 LDPE- Low density polyethylene

 Another plastic that is

considered a low hazard, LDPE
is used in bags for bread,
newspapers, fresh produce,
household garbage and frozen
foods, as well as in paper milk
cartons and hot and cold
beverage cups. While LDPE
does not contain BPA, it may
pose risks of leaching estrogenic
chemicals, similar to HDPE.
 PP- Polypropylene

 PP plastic is used to make

containers for yogurt, deli foods,
medications and takeout
meals. While polypropylene is
said to have a high heat
tolerance making it unlikely to
leach chemicals, at least one
study found that PP plastic ware
used for laboratory studies did
leach at least two chemicals.
 PS- Polystyrene

 A.k.a Styrofoam, is used to

make cups, plates, bowls, take-
out containers, etc.
 Polystyrene is known to leach
styrene, which can damage
your nervous system and is
linked to cancer.
 Temperature has a role in how
much styrene leaches from PS
containers, which means using
them for hot foods and
beverages (such as hot coffee
in a polystyrene cup) may be
worst of all.
 Acrylic, Polycarbonate, Nylon,
Fiber glass,
 BPA and BPS are endocrine
disrupters, which means they
mimic or interfere with your
body's hormones and "disrupts"
your endocrine system. The
glands of your endocrine
system and the hormones they
release are instrumental in
regulating mood, growth and
development, tissue function,
metabolism, as well as sexual
function and reproductive
processes.
Distinguishing Polymers
 Properties of Plastics

Thermoplastics are plastics that

soften when they are heated, then
harden again as they cool. They
mimic fats.
Thermoset plastics harden
permanently once molded for the
first time. Reheating may cause them
to decompose. They mimic egg
white. e.g.Bakelite, billiard balls
 Polymer Types
• Thermoplastic Polymers - Soften on reheating
• Thermosetting Polymer
– Set to an infusible solid and do not soften on reheating
 LDPE vs HDPE
LDPE HDPE
Soft, lighter, Harder, denser,
thermoplastic, low thermoset, more rigid,
melting higher melting
LDPE has more side HDPE chains are formed
chains or offshoots from without much branching
the main HC chain Molecules are closely
Chains are packed in a packed in an organized
very irregular manner like manner
tangled web There are more regions of
crystallinity
 Properties of plastics
The simple molecules making up the
polymer may be identical
(homopolymer) or different (copolymer).
The polymer chain may be linear,
branched, or cross-linked.
Cross-linking between polymer chains
adds more chemical bonds making the
polymer stronger and durable.
The molecules are prevented from
slipping past one another, even at higher
temperature.
 Homopolymers vs
Copolymers
Homopolymers Copolymers
LDPE PET
HDPE Polyformaldeh
PP yde
PS Nylon 66
PVC
Copolymers
 A copolymer contains two different kinds of monomer units.

H H H2 H2 H H H H2
H2C C C C C C H2C C C C

butadiene unit

styrene unit
segment of styrene-butadiene rubber (SBR)
 Properties of plastics

Polymers may form in two ways: by

joining together unconnected
monomers (addition
polymerization) or by joining
together monomer molecules and
in the process lose simple
molecules like water, alcohol or
acid (condensation
polymerization)
 Polymer Types
Addition Polymer
Produced by successive addition
reactions
Polyethylene is an example of an
addition polymer.

Condensation Polymer
Formed when monomers combine
and split out water or some other
simple substance.
Essentially a substitution reaction
Nylon is a condensation polymer.
 Addition Polymerization

• Addition polymerization starts with

monomers that contain C=C bonds.
•When these bonds react, each alkene
carbon bonds to another monomer.

H2C CH2 + H2C CH2 C C C C

 Rubber vs Gutta percha
Rubber has the cis Gutta percha has the
configuration (all trans configuration
(methyl groups which
methyl groups on are nearest neighbors
one side of the are on opposite sides of
polymer chain) the polymer chain)
It is an elastic rubber
Rubber, when
vulcanized, is used as Used as coating for
golf-balls, surgical
car tires, water hoses, equipment and elastic
etc. insulator for underwater
cables
 Vulcanization

Vulcanization removes the stickiness

of rubber. It retains its elasticity even
when heated and becomes more
resilient.
Vulcanization extends the useful
temperature range of rubber
products and imparts greater
abrasion resistance to them.
 Vulcanized Rubber
• The vulcanization process is usually accomplished by heating
raw rubber with sulfur and any other auxiliary agents. (about
3.5%)
• Ebonite or hard rubber which is used for making black piano
keys and casings of car batteries is rubber which has been
vulcanized to the extend of 68% sulfur.
CH3 CH3
H H H
H2C C C CH C C C

S S

S S
H H
CH C C CH C C

CH3 CH3
 A. Hydrocarbon plastics
PE, PP and PS have excellent electrical
insulating material.
This is because there are no mobile electrons
in these polymers
They are trapped in the C-C and C-H bonds
Electrical current cannot flow through the
solid
HC chains re electrically uniform or neutral
and are not affected by alternating current
Polyethylene- PE
 Types: HDPE, LDPE, LMWPE
 PE is a thermoplastic polymer heavily used in consumer products
(over 60 million tons are produced worldwide every year).
 Its name originates from the monomer ethene, commonly known
as ethylene.
 Polyethylene (other than cross-linked polyethylene) usually can
be dissolved at elevated temperatures in aromatic hydrocarbons
(i.e. toluene, xylene) or chlorinated solvents (i.e. trichloroethane,
trichlorobenzene).
 Low Density Polyethylene -
LDPE
Low-density polyethylene (LDPE) is a
thermoplastic made from oil.
LDPE is defined by a density range of 0.910 -
0.940 g/cc.
It is unreactive at room temperatures,
except by strong oxidizing agents.
It can withstand temperatures of 80 °C
continuously and 95 °C for a short time.
Made in translucent or opaque variations, it
is quite flexible, and tough to the degree of
being almost unbreakable.
Low Density Polyethylene -
LDPE
 It has more branching (on about 2%
of the carbon atoms) than HDPE, so
its intermolecular forces are weaker.
 Since its molecules are less tightly
packed and less crystalline because
of the side branches, its density is
lower.
 LDPE is widely used for manufacturing
various containers, dispensing bottles,
wash bottles, tubing, and various
molded laboratory equipment. Its
most common use is in plastic bags.
 High Density Polyethylene -
HDPE
 HDPE has little branching, giving it stronger
intermolecular forces and tensile strength
than lower density polyethylene.
 It is also harder and more opaque and can
withstand somewhat higher temperatures
(120° Celsius for short periods, 110° Celsius
continuously).
 The lack of branching is ensured by an
appropriate choice of catalyst (e.g. Ziegler-
Natta catalysts) and reaction conditions.
 High Density Polyethylene -
HDPE
 HDPE is resistant to many different solvents and has
a wide variety of applications, including:
 Containers
Tupperware, Laundry detergent
bottles,Milk cartons, Fuel tanks for cars
 Plastic bags
 Containment of certain chemicals
 Chemical-resistant piping systems
 Geothermal heat transfer piping systems
 Natural gas distribution pipe systems
 Water distribution pipe systems
 One of the largest uses for HDPE is wood plastic
composites.
 Polypropylene polymer- PP
PP is a thermoplastic polymer
used in a wide variety of applications,
including food packaging, textiles, reusable
of various types, laboratory equipment,
loudspeakers, automotive components,
An addition polymer made from the
monomer propylene, unusually resistant to
many chemical solvents, bases and acids.
Polypropylene polymer- PP

•Its resin identification

code is

Can withstand autoclaving

B. Polyvinyl Polymers

 General formula of repeating unit of polyvinyl polymers

H X
| |
-C – C-
| |
H H n

 General formula of repeating unit for polyvinyl chloride

Polyvinyl chloride - PVC

 Polyvinyl chloride. commonly

abbreviated PVC, is a widely-used
plastic.
 Globally, over 50% of PVC manufactured
is used in construction. It has been
replacing traditional building materials
such as wood, concrete and clay in
many areas.
 Despite appearing to be an ideal
building material, concerns have been
raised about the costs of PVC to the
natural environment and human health.
Polyvinyl Polymers -PVC

 There are many uses for PVC. As a hard plastic, it is

used as vinyl siding, magnetic stripe cards, window
profiles, gramophone records (which is the source of
the name for vinyl records), pipe, plumbing and
conduit fixtures.
 It can be made softer and more flexible by the
addition of plasticizers, the most widely used being
phthalates. In this form, it is used in clothing and
upholstery, and to make flexible hoses and tubing,
flooring, roofing membranes, and electrical cable
insulation.
 Often used for pipelines in the water and sewer
industries because of its inexpensive nature and
flexibility.
Examples of plastic bottles

HDPE LDPE PVC

C. Polyacrylates

 Acrylic acid has the structure:

O
||
CH2=CH-C-OH
 The polymer of its methyl ester is used
as base for acrylic paints which are
formed simply by adding pigment.
 After applying these paints on a
surface, it forms a rubbery, flexible
film as the water evaporates from the
surface.
Polyacrylates

Methyl cyanoacrylate is the substance in

“Super glue” (it is not yet polymerized)
When spread on surface with electron
rich groups (wood, paper, etc)
containing traces of water or alcohol, it
starts to polymerize.
Because of he bulky irregular nature of
the substituent groups, the molecules do
not pack closely. There are lots of
spaces which are filled and lock the
surfaces when joined
See table for structure
D. Condensation polymers

 The first synthetic polymer was prepared by Leo

Hendrik Baekeland in 1909 from the polymerization of
phenol and formaldehyde
 Other examples are Nylon and polyethylene
terephthalate
Bakelite plastics

Bakelite is hard, sturdy, thermoset,

resistant to heat and electricity
because cross-linking between
chains at several positions
produces a three-dimensional
structure that is hard, sturdy,
resistant to abrasions, and has
electrical insulating property.
E. Synthetic Fibers

Synthetic fibers are polymers of high

tenacity: they have high ratio of length
to diameter
Fibers that are spun into yarn must have
high tenacity or tensile strength.
Molecules must lie parallel to other as
they are drawn into threads
The process involves extruding the
molten polymer solution through a
spinneret and stretching to several times
its original length.
 Synthetic fibers
On stretching, the molecules are made
parallel to each other in a very
organized manner.
Polyethylene terephthalate is noted for
its high crease resistance because the
bulky benzene ring is part of the chain
which adds stiffiness to the chain
Development of Plastics

DATE EVENTS
1839 Charles Goodyear accidentally discovered the process of
vulcanization
1846 Christian Schoenbein accidentally invented guncotton or
nitrocellulose
1863 John Hyatt produced celluloid (articificial ivory) from a mixture
of camphor and lightly nitrated cellulose and was
manufactured commercially in 1870
1909 Leo Hendrick Bakeland the first synthetic organic polymer
(phenolformaldehyde or Bakelite plastics)
1930’s Styrene-butadiene rubber developed by German chemists
Wallace Carothers developed Neoprene (synthetic rubber from
chloroprene) forcommercial production
Development of Plastics

DATE EVENTS

1934 Polyethylene first prepared at Imperial Chemicals in

Great Britain
1938 Teflon first prepared at Dupont

1946 John Rex Winfield produced the polyester PET from

ethylene glycol and terephthalic acid
1950 Karl Ziegler produced high density polyethylene in
Germany
1953 Karl Ziegler and Giulio Natta prepared independently
the first stereochemically ordered polyproplyene
1963 Karl Ziegler and Giulio Natta received Noberl prize in
Chemistry
 Hazards from Burning Plastics
Most products from synthetic polymers burn
at elevated temperatures. Many such
products are used as building materials or
articles in our homes.
Generally, there are 3 significant burning
characteristics associated with plastics:
1. The plastic product often melts as it burns
2. The plastic surface tends to char and
disintegrate.
3. The burning plastic polymer evolves large
amounts of smoke, carbon monoxide and
other toxic fire gases.
 Hazards from Burning Plastics

Melting can contribute to the spread

of fire from its source to elsewhere.
Polymeric materials also conduct or
radiate heat causing thermal
degradation at different points, the
degradation can produce a
combustible mixture of simple
organic substances which can ignite
any time.
 Hazards from Burning Plastics
Fatalities in burning buildings
involving plastic polymers are
usually caused by inhalation of fire
gases, as opposed to burns and
other causes.
In a small room, the
concentration of fire gases can
easily reach life threatening levels
in a matter of seconds.
 Hazards from Burning Plastics
Fire gases include carbon dioxide,
carbon monoxide, HCl, HCN,
Ammonia, and acrolein.
Acrolein is an unsaturated aldehyde
(CH2=CHCHO), it is a powerful irritating
lachrymator. Its theshold limit value
(TLV) is only 0.1 ppm.
 Hazards from Burning Plastics
Plastic Polymers Fire gases that may produce on
burning

1. Polyethylene CO
2. Polyvinyl chloride HCl

3. Polyacrinonitrile HCN
4. Vulcanized rubber SO2
5. Nylon NH3, NO2
6. Teflon HF
7. Polyurethane NO2
8. Polystyrene CH4, ethene, ethane, benzene, toluene
(all are combustible and can easily
ignite)
 Plastic Wastes
Plastics are synthetic products whose
chemical bonds have been made so
strong that as a rule they do not
degrade in the environment.
How do we deal with plastic wastes?
- The theme used in dealing with
plastic wastes is REDUCE, REUSE AND
RECYCLE.
 Assignment (Group work)
1. We use polyethylene bags as containers for wet
food because the plastic repels ions and water.
But grease, fats and oils stains on plastics. Explain
these observations in terms of the structure of
polyethylene.
2. Polymethyl methacrylate (Lucite or Plexiglass) is
used for windshields, aircraft windows, and
optical lenses because of its transparency. Study
the structure of the polymer and explains its
transparency.
3. SARAN is the cling wrapping for food and other
materials we use at home. Explain what makes it
useful for this purpose.
4. PTFE or Teflon is one of the most slippery
substance known. This makes it useful as nonstick
coatings on pans and as dry lubricant for
bearings and other similar applications. Explain
this observed property of Teflon.