Polymers, Plastics and Rubbers

What is a polymer?

Polymers are large molecules made up of long chains of atoms

covalently bonded together.

Monomers (from mono meaning “one” and meros meaning

“unit”) are the small molecules used to synthesize the polymeric
chain, like a strand of paper clips.

9.2
The polymers (poly means “many”) can be formed from the
same type of monomer or from a combination of monomers:

(a) A representation of a monomer.

(b) A representation of a polymer made of one monomer.
(c) A representation of a polymer made of two different monomers.

9.3
Polymers are referred to as macromolecules because they
involve thousands of atoms, and their molecular masses can
reach over a million.
Many common classes of polymers are composed of hydrocarbons.

Carbon makes up the backbone of the molecule and hydrogen atoms

are bonded to the carbon atoms. Below is a diagram of polyethylene,
the simplest polymer structure.
H H H H H H

C C C
* C C *

H H H H
n
polyethylene

Other examples of polymers that contain only carbon and

hydrogen include polypropylene, polybutylene, and polystyrene.
9.3
Types of polymers according to
polymerization process

•Addition polymers
•Condensation polymers

No other products are formed, and no atoms are eliminated.

9.3
In addition polymers, the monomers simply add to the growing
polymer chain in such a way that the product contains all the
atoms of the starting material.
H H H H
H H
2 C C C C C C
H H
H H H H
ethylene addition product
monomer

As additional ethylene molecules join, the chain grows:

H H H H H H H H H H
H H
C C + C C C C C C C C C C
H R
H H H H H H H H H H

No other products are formed, and no atoms are eliminated.

9.3
 The overall process can be represented as:

H H
H H
n C C C C

H H H H n

If one of the H atoms on ethylene is replaced with a Cl atom,

H H
H H
n C C C C

H Cl H Cl n

the result is the formation of polyvinyl chloride (PVC).

9.3
 Condensation Polymers

Formation of PET

Examples
Ester linkages Natural: starch, wool, silk, proteins
highlighted in blue
Synthetic: nylon, kevlar, and ABS
9.6
 POLYMERS
Polymers can be divided into 2 types :

 naturally occurring polymers

 synthetic polymers
 naturally occurring polymers
Polymers that exist in plants or animals

Types of naturally occurring polymers

 protein : muscles
 carbohydrates : cellulose
 natural rubber : latex
 synthetic polymers

Polymers made in industry from chemical

substances

Scientists are able to copy structures of

natural polymers to produce synthetic
polymers trough scientific research
 synthetic polymers
many of raw materials for synthetic polymers
are obtain from
-> petroleum
types of synthetic polymers
 plastics
 fibers
 elastomers
Overview
PLASTIC IS THE DEVIL’S MATERIAL
PLASTIC IS BAD FOR THE ENVIRONMENT
PLASTIC CAUSES CANCER
PLASTIC KILLS SEA TURTLES
PLASTIC SHOT MY DOG (JOKING)
The relentless attacks on the plastics industry are Image courtesy of Turtle Bags
based primarily on perception – not fact.

The plastics industry did not throw those bags into

the ocean or trees – people did.

If those bags had been recycled, none of these

pictures would have been possible
Image courtesy of the City of Los Angeles
Overview
Many of the same properties that make plastics such a valuable
resource also make it a target for environmental groups.
• Plastics are durable and chemically resistant
-They don’t degrade easily
• Plastics are lightweight
-They will blow around and get stuck in trees and other plant life
- Some float and are visible when they are polluting waterways

It’s not the plastic that is the problem, it is the people who are not
disposing of them properly. To me, that is not a problem with our
INDUSTRY, it is a problem with our SOCIETY.
Plastic or Glass?
Making containers out of plastic instead of glass leads to reductions in
fuel costs and emissions as well.
Lets look at mustard
Glass Plastic

Weight Weight
(oz.) % (oz.) %
Mustard 9.0 64 8.0 86
Package 5.0 36 1.3 14
14.0 100 9.3 100
71% less packaging per ounce of product
Plastic or Glass?
Peanut Butter anyone?

Glass Plastic
Weight of the jar: 10.2 oz. 1.7 oz.
% of total weight
that’s product: 64% 91%
Shipping and energy comparison: you can ship the same amount of
peanut butter in 2 tractor trailers that you would need to ship in 3
tractor trailers if you use plastic packaging instead of glass
Paper or Plastic?
Whenever I go to the grocery store, and the cashier asks me whether I
want paper or plastic bags, I ALWAYS reply, “Plastic, because it’s better
for the environment.”
Usually I get either a dumb look or a chuckle, but every once in a while I
get someone who will start to argue with me, and then it’s GO TIME.
• It takes 7 semi’s to ship the same amount of paper bags as it does to
ship plastic bags. That’s 7X the amount of fuel consumed and
emissions into the atmosphere.
– 1,000 paper bags weigh 140 lbs (46 in high)
– 1,000 plastic bags weighs 16 lbs (4 in high)

Wow, those’re some heavy paper

bags! Image courtesy of theliar.
Paper or Plastic?
• Plastic bags consume only 18% of the energy required to make paper
bags. Most energy production plants burn fossil fuels to produce their
energy, they don’t run on fairy dust.
• Plastic bags use only 3% of the fresh water required
to make paper bags.
• Plastic bags produce 80% LESS waste than paper
bags. That means that it takes 5X the number of
garbage trucks to carry the same number of paper
bags to the dump as 1 truck of plastic bags.

• It takes 91% less energy to recycle one pound of

plastic bags when compared to one pound of paper
Recycling
There are 7 primary recycling symbols
They are listed at the left. The most
commonly recycled materials are
PETE (Polyester), polyethylene, and
polypropylene.

Polyester is commonly recycled into

carpeting and polyethylene bags are recycled into
more bags.

Many times polyethylene and polypropylene recycled

materials are mixed and molded into items like
flower pots or plastic lumber.
Recycling
Regardless of how much we reduce the amount of plastic materials in
products and how efficient we make the designs, there will still be
material that needs to be recycled and reused.
One of your challenges in the industry will probably
be to identify areas where this material can be
utilized.
There are many components that are not as
dimensionally or functionally demanding that this
material can be used for. There are applications in
every industry where recycled materials can be
used.
Coming up with innovative ways to utilize this ‘waste’
makes companies more efficient and can save money.
Biodegradable
Some of the first plastic materials created were from agricultural
sources – rubbers, cellulosic, and casein.
Today, many of the newer polymers that are being developed are being
created from starches. Mainly corn and potato.
Polylactic acid is produced from corn starch and has many properties
similar to that of Polyester Terephthalate. It is more difficult to
process and is more easily degraded by higher temperatures, but the
material shows potential.
 FACT OR MYTH?
When you eat or drink things stored in plastic, is plastic
incorporated into you?

MYTH
Plastic does not seem to affect human health; HOWEVER,
it can dangerously effect other animal life and alter the
environmental (air, water, and soil) causing hazardous pollution
when it is dumped into the environment.

23
 Can Plastics Kill?
•Birds and turtles are killed
every year from plastic bag litter in
the aquatic environment as they
often mistake plastic bags for food.

•Plastic bags, once ingested,

cannot be digested or passed by an
animal so it stays in the gut.

• Plastic in an animal’s gut can

prevent food digestion and can lead
to a very slow and painful death.

24
 Plastics: Friend or Foe?
Plastic is ubiquitous in our lives because it is convenient and
Relatively inexpensive. It is convenience comes from being
lightweight and its ability to absorb impact shock without breaking,
which on its own merit, is hard to argue with.
Plastics are so versatile in use that their impacts the
environment are extremely wide ranging, posing serious challenge for
disposal

25
 When Can It Become a Problem?
Careless disposal of plastic bags chokes drains, blocks
the porosity of the soil, and causes problems for groundwater
recharge.. Due to its non-biodegradable nature,
littering of plastics causes irreversible damage to the
environment.

Municipalities routinely receive reports

of death of cows and other animals from
ingesting plastic bags.

26
 ALTERNATIVES

Plastic bags take between 15 to 1000 years to degrade.

The chemical pollutants released from them are a Serious Threat
to be Tackled.

Designing eco-friendly, biodegradable plastics is the need of

the hour. Though partially biodegradable plastics have been
developed and used, completely biodegradable plastics based on
renewable starch rather than petrochemicals have only recently
been developed and are in the early stages of commercialization.

Paper , Cloth, Jute, Cane, etc.,

are the most preferable but still
controversial

27
 plastics

composed of polymers of carbon and

hydrogen alone or with oxygen, nitrogen,
chlorine or sulfur in the backbone
 plastics
Properties of plastics :-
 Light
 strong
 malleable
 inert to chemical
 insulators of electricity
and heat
 plastics
 example of plastics are :-
 polythene (polyethylene)
 polyvinylchloride (PVC)
 polypropene (polypropylene)
 polystyrene
 Perspex
 Bakelite
31
Thermoplastics materials
These are described as plastics that can be
reformed using heat : this plastic has a memory,
it returns to its original flat shape when re-heated.
When cooled they become hard and rigid once
again.
Example: Polyethylene, PVC, Nylon
Uses: Bags,
Here are someMugs, Toys
examples and their uses : Polypropylene

Acrylic – available in almost any colour in sheet rod

or tube form, can be shaped using a line bender or
vacuum former.

ABS (Acrylonitrile Butadiene Styrene) – a very commonly used plastic can be injection moulded from a powder form.

Styrene – very good for vacuum forming.

thermoplastic resin. ABS.

Thermosetting materials Kettle saucepan
handles
These are described as plastics that do not
reform using heat, they “SET” and cannot
be reshaped .

Here are some examples and their uses :

Urea formaldehyde – electric plugs and

sockets

Melamine – kitchen worktops,

unbreakable drink mugs

Polyester resin – poured into moulds to

make products or for boat repair
Harry Allen’s paper weight/doorstop made

from resin
 Difference between Thermoplastics & Thermosetting plastics

S.No. THERMOPLASTICS THERMOSETTING PLASTICS

1. Formed by addition Polymn. Formed by condensation Polymn.

2. Long chain linear polymers Three dimensional network

structure joined by strong covalent
bonds

3. Soften on heating and stiffen on Do not soften on heating

cooling
4. Can be remoulded Cannot be remoulded
5. Usually soft, weak & less brittle Usually hard, strong & more brittle

6. Can be reclaimed from wastes Cannot be reclaimed from wastes

7. Soluble in organic solvents Insoluble in organic solvents

35
 Polyvinyl Chloride (PVC)
 Specific gravity about 1.39
 It’s made from monomer, vinyl chloride
 Tensile strength low nearly like polystyrene
 It’s an excellent insulator
 Used in raincoats and shower curtains
 Extensively used in floor tiles, electric
cables, flexible sheeting, hoses, pipes,
expansion joint filler,moldings, luggage,
decorative wall coverings,
Multi-Lock Industrial Warehouse Floor Tile Made Using PVC
PVC Vinyl Floor Tile
PVC pipe
Electrical insulation
characteristics of PVC
The electrical characteristics of PVC such as
electrical insulating properties or dielectric
constant are excellent.

To express electrical insulating properties, volume resistivity or

dielectric strength is widely used as an index. The volume resistivity is
expressed in terms of electrical resistance calculated per unit volume of
the test piece. The dielectric strength is expressed in terms of the
magnitude of voltage withstood without destruction of the test piece
when a specified amount of voltage is applied for a specified period of
time. In both cases, a higher value means better electrical
characteristics.
Electrical insulation characteristics
of PVC
As shown in the Charts, the volume
resistivity of PVC products is slightly
lower
than those of olefin resin products, but
since higher fire resistant properties are
required for electrical components,
PVC is used widely in a variety of
applications such as electric cables for
residential buildings, vehicles,
household electrical appliances, cable
coverings, insulating tapes, switch
boxes, wire coverings, and protecting
tubes for power and
telecommunications cables.
 Types of Rubber
– Natural rubber (NR): agricultural crop
– Synthetic rubbers: prepared from petroleum
• Production of raw NR is an agricultural industry
because latex, the starting ingredient, is grown
on plantations in tropical climates
• By contrast, synthetic rubbers are produced by
the petrochemical industry
• Finally, processing into tires and other products
occurs at processor (fabricator) plants,
commonly known as the rubber industry
• Natural rubber is tapped from rubber trees
(Hevea brasiliensis) as latex
– In Southeast Asia and other parts of the world
• Latex is a colloidal dispersion of solid
particles of the polymer polyisoprene in
water
– Polyisoprene (C5H8)n is the chemical
substance that comprises NR, and its content
in the emulsion is about 30%
• Preferred method to recover rubber from latex
involves coagulation - adding an acid such as
formic acid (HCOOH)
– Coagulation takes about 12 hours
• The coagulum, now soft solid slabs, is then
squeezed through rolls which drive out most of the
water and reduce thickness to about 3 mm (1/8 in)
• The sheets are then draped over wooden frames
and dried in smokehouses for several days
• The resulting rubber, now in a form called ribbed
smoked sheet, is folded into large bales for
shipment to the processor
• In some cases, the sheets are dried in hot air
rather than smokehouses, and the term air‑dried
sheet is used
– This is considered a better grade of rubber
• A still better grade, called pale crepe rubber,
involves two coagulation steps, followed by warm
air drying
• Most synthetic rubbers are produced from
petroleum by the same polymerization
techniques used to synthesize other polymers
• Unlike thermoplastic and thermosetting
polymers, which are normally supplied to the
fabricator as pellets or liquid resins, synthetic
rubbers are supplied to rubber processors in
the form of large bales
– The rubber industry has a long tradition of handling NR in
these unit loads
 Compounding
• Rubber is always compounded with
additives
– Compounding adds chemicals for vulcanization,
such as sulfur
– Additives include fillers that either enhance the
rubber's mechanical properties (reinforcing fillers)
or extend the rubber to reduce cost (non‑reinforcing
fillers)
– It is through compounding that the specific rubber is
designed to satisfy a given application in terms of
properties, cost, and processability
 Carbon Black in Rubber
• The single most important reinforcing filler
in rubber is carbon black, a colloidal form
of carbon obtained by thermal
decomposition of hydrocarbons (soot)
– It increases tensile strength and resistance to
abrasion and tearing of the final rubber product
– Carbon black also provides protection from
ultraviolet radiation
– Most rubber parts are black in color because of their
carbon black content
 Other Fillers and Additives in
Rubber
• China clays ‑ hydrous aluminum silicates
(Al2Si2O5(OH)4) reinforce less than carbon black but are
used when the color black is not acceptable
• Other polymers, such as styrene, PVC, and phenolics
• Recycled rubber added in some rubber products, but
usually 10% or less
• Antioxidants; fatigue‑ and ozone‑protective chemicals;
coloring pigments; plasticizers and softening oils;
blowing agents in the production of foamed rubber;
mold release compounds
 Mixing
• The additives must be thoroughly mixed with
the base rubber to achieve uniform dispersion
of ingredients
• Uncured rubbers have high viscosity so
mechanical working of the rubber can
increase its temperature up to 150C (300F)
• If vulcanizing agents were present from the
start of mixing, premature vulcanization would
result ‑ the “rubber processor's nightmare”
 What is Vulcanization?

The treatment that accomplishes cross‑linking of

elastomer molecules
• Makes the rubber stiffer and stronger but retain
extensibility
• The long‑chain molecules become joined at certain
tie points, which is reduces the ability to flow
– Soft rubber has 1 or 2 cross‑links per 1000 mers
– As the number of cross‑links increases, the polymer
becomes stiffer (e.g., hard rubber)
 Effect of Vulcanization on
Rubber Molecules

(1) raw rubber, and (2) vulcanized

(cross‑linked) rubber: (a) soft rubber and
(b) hard rubber
Vulcanization Chemicals and
Times
• When first invented by Goodyear in 1839,
vulcanization used sulfur (about 8 parts by weight of
S mixed with 100 parts of NR) at 140C (280F) for
about 5 hours
– Vulcanization with sulfur alone is no longer used, due to long
curing times
• Various other chemicals (e.g., zinc oxide, stearic
acid) are combined with smaller doses of sulfur to
accelerate and strengthen the treatment
– Resulting cure time is 15‑20 minutes
 The history of synthetic rubber
The first rubber tyres were produced in 1791.
Around 1820 Thomas Hancock invented the
‘pickling machine’, that masticated rubber and
turned it into a warm, homogenous mass. The
big breakthrough in the use of rubber for tyres
came in 1839 when Charles Goodyear
invented vulcanised rubber.
 The history of synthetic rubber (2)

The demand for rubber increased rapidly.

During the 19th century Brazil held the
monopoly on natural rubber. However, with
the legal export of seeds of the rubber tree
(Hevea brasiliensis) to England, later to
Ceylon (Sri Lanka) and Malacca, the
production of natural rubber in South East
Asia soon exceeded the Brazilian production.
The history of synthetic rubber (3)

Synthetic rubber was already invented around

1910 but it took until WWII before it was
produced on a larger scale. The supply of
natural rubber from South East Asia was
halted due to the Japanese occupation of South
East Asia.
The history of synthetic rubber (4)

Japan had been feeding their war machine since 1931

(Japanese occupation of South East Asia) and
desperately needed rubber.

The plan was simple: send an army and occupy all

rubber plantations. The Japanese attack on Pearl
Harbour (7 December 1941) cut off nearly all of the US
sources of natural rubber, the only natural resource the
US does not have. A day later the Malayan peninsula
was invaded, securing Japanese access to vast rubber
reserves and more enemies than it could cope with.
The history of synthetic rubber (5)

After WWII, the production and supply of natural

rubber was quickly restored. Due to the increasing
price and demand, by the 1960s the production of
synthetic rubber soon surpassed that of natural
rubber. The demand for rubber increased even
further; in the 1970s following the strong growth in
the car industry and in the 1980s due to the
increasing demand for condoms as a result of the
worldwide AIDS epidemic (most condoms contain
natural rubber).
 Types of synthetic rubber
Styrene Butadiene Rubber (SBR) and
Butadiene Rubber (BR) are the most widely
consumed types of synthetic rubbers.
Butadiene rubber is fully substitutable by
natural rubber (NR) regarding its use in tyres.
Emulsion Styrene Butadiene Rubber (ESBR)
and BR are both used for tyres, whereas
Solution Styrene Butadiene Rubber (SSBR) is
used for asphalt applications.
 Synthetic rubber applications
Figure 1 : global SBR applications
Based on a presentation during Rubber Summit, Ontario, 2008
Global SBR applications

mechanical goods
15%
automotive parts
5%
others
4%

tyres
76%
Figure 2 : Global PBR applications
Based on a presentation during Rubber Summit, Ontario, 2008

Global PBR applications

impact modifier
25%

others
4%
golf balls
tyres 1%
70%
Figure 3 : World tyre production
Based on a presentation during Rubber Summit, Ontario, 2008

World Tyre production

global production in
million units/year
2000
1800
1600
1400
1200
1000
800
600
400
200
0
2007 2008 2009 2010 2011 2012

USA Western Europe CIS Japan South Korea China

 NATURAL AND SYNTHETIC RUBBER

PRESENTED BY: Y.MANASA(B130756CH) YOGESH KUMAR(B130983CH) AJAY

KRISHNAN V(B120652CH)
 Elastomers are used in wide variety of industrial, medical and
household products and major portion of elastomers consumption
goes into tyres next largest product sector is latex goods.
 There are two major types of elastomers; natural rubber a product of
tropical tree Hevea brasiliens is and synthetic rubber- a family of
materials derived from petrochemical feed stocks[Chemistry &
industry 5, August 1996, p.574]. Major producers of natural rubber are
natural rubber producing country are Thailand, Indonesia and
Malaysia, Africa, Latin America, Brazil,Cambodia, Nigeria, Sri Lanka,
Thailand, India.
 Demand for natural is estimated to have been around 10.9 million
tones in 2011 out of which around 45 percent was from Asia. About
92percent of natural rubber is produced from Asian countries. The
demand for natural rubber globally is projected to grow by 3-4percen
through 2014.
 Synthetic rubbers have slowly replaced natural rubbers and have
undergone variousdevelopments for applications in automotives,
chemical industry, energy generationSports,aerospace industry,etc .
 Natural rubber, also called India rubber or caoutchouc, as

initially produced, consists of polymers of the organic

compound isoprene, with minor impurities of other organic
compounds plus water. Forms of polyisoprene that are used
as natural rubbers are classified as elastomers. Currently,
rubber is harvested mainly in the form of the latex from
certain trees. The latex is a sticky, milky colloid drawn off by
making incisions into the bark and collecting the fluid in
vessels in a process called "tapping". The latex then is refined
into rubber ready for commercial processing. Natural rubber
is used extensively in many applications and products, either
alone or in combination with other materials. In most of its
useful forms, it has a large stretch ratio and high resilience,
and is extremely waterproof.
 Synthetic rubber, invariably a polymer, is any type of artificial
elastomer mainly synthesised from petroleum byproducts. An
elastomer is a material with the mechanical (or material) property that
it can undergo much more elastic deformation under stress than most
materials and still return to its previous size without permanent
deformation. About 15 billion kilograms of rubbers are produced
annually, and of that amount two thirds is synthetic. Global revenues
generated with synthetic rubbers are likely to rise to approximately
US$56 billion in 2020.
 Synthetic rubber, like natural rubber, has uses in the automotive
industry for tires, door and window profiles, hoses, belts, matting,
flooring and dampeners (antivibration mounts).
 Styrene butadiene rubber is most widely used elastomer in the
world.SBR is used forboth tire and non-tire application Styrene
butadiene rubber known as Buna-S was first prepared by I.G.
 Farbenindustrie in Germany. There has been significant
development in the process technology of styrene butadiene
rubber manufacture. Amongst the various processes,
emulsion polymerisation of SBR is most commonly used. The
cold process of emulsion polymerisation process has replaced
the hot polymerisation process. In India, first SBR manufacture
was started by Synthetic and Chemicals, Bareilly in 1963,
however, the unit has been closed presently.
 Although butadiene is recovered from cracker plant, it can be
also made from ethanol route.
 Styrene is made from ethyl benzene by alkylation of benzene
with ethylene which can be also recovered from FCC gases.
  There are tow conventional
routes
to producing solid SBR:

 Hot emulsion polymerization

 Cold emulsion polymerization

 Hot emulsion polymerization is the original SBR process. The
major characteristic of this process is that these grades have
exceptional processing characteristics in terms of low mill
shrinkage, good dimensional stability and good extrusion
characteristics.

 However, high levels of micro-gels are also produced, so

there is a trend towards using the cold emulsion
grades in many applications.

 However, they are still used in applications

such as adhesives and flow modifiers for other elastomers
where good flow properties are required.
 Cold emulsion polymerization produces SBR grades
with superior mechanical properties, especially
tensile strength and abrasion resistance, compared
to the grades produced by the hot emulsion
polymerization process.

 This process has largely replaced the hot emulsion

polymerization process for production of e-SBR
grades.