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
 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.
 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.
 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
 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
 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.
 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
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, thermoplastic, Harder, denser, thermoset,
low melting more rigid, higher melting
LDPE has more side chains or HDPE chains are formed
offshoots from the main HC without much branching
chain Molecules are closely packed
Chains are packed in a very in an organized manner
irregular manner like tangled There are more regions of
web 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 • Polyformaldehyd
• PP e
• 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
• Addition Polymer Types
– 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 trans
configuration (all methyl configuration (methyl groups
groups on one side of the which are nearest neighbors
are on opposite sides of the
polymer chain) polymer chain)
Rubber, when vulcanized,It is an elastic rubber
is used as car tires, water Used as coating for golf-
balls, surgical equipment
hoses, etc. and elastic 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 - 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
 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.