THE PLASTICS, RUBBER AND FIBRES

(POLYMERS)
 What are Polymers ?
They are high molecular weight compounds built up
by the repetition of small chemical units known as
monomers.
Natural
Polymers rubber, cellulose, wool, starch and proteins.

Synthetic i.e.
PVC,PE,PET,PS
 Cont’d
 The term polymer comes from two Greek words: “polys”
which means “many” and “meros” which means “parts.”
 A polymer is therefore a high molecular weight compound
made up of hundreds or thousands of many identical small
basic units (monomers) of carbon, hydrogen, oxygen or
silicon atoms.
 The monomers are linked together covalently in a chemical
process known as polymerization.
 Cont’d

Repeating Unit(monomer): The repeating unit of a linear

polymer is a portion of the macromolecule such that the
complete polymer (except for the ends) might be produced
by linking a sufficiently large number of these units through
bonds between specified atoms.
 Cont’d

 A monomer is a molecule that combines with other

molecules of the same or different type to form a polymer.
 The repeating unit may comprise a single identifiable
precursor as in polystyrene, polyacrylonitrile, polyethylene,
or poly(vinyl chloride).
 Cont’d

 An Oligomer is a low-molecular-weight polymer. Oligomer

of polyethylene: (n-CH3—(CH2)29—CH3)
 It contains at least two monomer units.
 Generally speaking, a species will be called polymeric if
articles made from it have significant mechanical strength
and oligomeric .
 The distinction between the sizes of oligomers and the
corresponding polymers is left vague because there is no
sharp transition in most properties of interest.
 Uses of polymers
 Polymers are involved in all of the major new technologies
including synthetic blood and skin, computer chips, CDs, liquid
crystals, and circuit boards-information visualization, storage
and retrieval; energy creation, storage and transmission(portable
electrical power (batteries),
 Efficient light and low-emission transportation, high temperature
superconductors, medicines,
 Targeting and control of drug delivery, and synthetic limbs and
other replacement parts, transportation, space craft, solar and
nuclear energy and photonics (optical fibers).
 Nomenclature of polymers

 Because of the diversity and universality of polymeric

materials there existed few guiding principles in the naming
of polymeric materials as polymers were emerging.
 Common Names: based on the place of origin $ named
after the discoverer.
 Hevea brasiliensis means ‘’rubber from brazil’’ and
Bakelite which is a three-dimensional polymer synthesized
from the reaction of phenol and formaldehyde, was
discovered by Leo Baekeland.
 Cont’d
 Source-Based Names:- based on the common name of the
reactant monomer preceded by the prefix poly.PVC,
PE,PET(hybrid of a source-based named ).
 Cont’d
 Structure-Based Names:- While the majority of common
polymers are known by common or source-based names,
 The "correct" or so-called scientific names are based on
rules described by the international body responsible for
systematic nomenclature of chemical compounds.
 IUPAC and others have published a series of reports for
naming polymers that are used for more complex polymers.
 Cont’d
 Linkage-Based Names:- Many polymer "families" are
referred to by the name of the particular linkage that
connects the polymers.
 The family name is "poly" followed by the linkage name.
polyester, polyamide…
 Trade names, Brand names and Abbreviations:-They
may be used to identify the product of a manufacturer,
processor or fabricator and may be associated with a
particular product or with a material or modified material.
 Classification of polymers
 Polymer are classified based on :-

 heat dependency, molecular structure and polymerization reaction

mechanisms.

 Addition and condensation Polymerization:- The

chemical reaction in which high molecular mass molecules are
formed from monomers is known as polymerization.
 There are two basic types of polymerization, chain-reaction

(or addition) and step-reaction (or condensation)

polymerization.
 Cont’d

 Chain-Reaction (addition) Polymerization:- This type of

polymerization is a three step process involving two
chemical entities. In nearly all cases, the monomers have at
least one carbon-carbon double bond.
 The monomer itself link in a polymer or another reactant
(catalyst i.e. a radical peroxide) added in low concentration .
H H
with ( )
C C Ethylene R O O R R O +R O representing
the free electron
H H
 Cont’d

Step 1:- Initiation: occurs when the free-radical catalyst

reacts with a double bonded carbon monomer, beginning the
polymer chain.
 The double carbon bond breaks apart, the monomer bonds
to the free radical
H H H H

R O +C C R O C C

H H H H
 Cont’d

 Step 2: Propagation:- is a repetitive operation in which

the physical chain of the reactive polymer is formed.

 Simply put, the single bounds in the polymeric chain are
more stable than the double bonds of the monomer so that,
it is thermodynamically favored.

R O CH2 CH2 +CH CH R O CH2 CH2 CH2 CH2

2 2

Propagating Monomer New Polymer

Polymer chain chain
 Cont’d
Step 3: Termination:- occurs when another free radical
(R-O.), left over from the original splitting of the organic
peroxide, meets the end of the growing chain or
 When two unfinished chains bond together
 This reaction produces a complete polymer chain
 This exothermic reaction occurs extremely fast, forming
individual chains of polyethylene often in less than 0.1
second.
 Cont’d
 Polymers created have relatively high molecular weights
R - O - CH2 - CH2 - CH2 - CH2 + R - O R - O- CH2 - CH2 - CH2 - CH2- O- R

left over free-

Propagating radical Completed
Polymer chain polymer
chain

R - O- CH - CH2 + R - O - CH - CH R - O - CH2 - CH 2 - CH2 - CH - O- R

2 2 2 2

Propagating Completed
Polymer polymer
chains chain
 Step-Reaction (condensation) Polymerization
 This polymerization method typically produces polymers of
lower molecular weight than chain reactions and requires
higher temperatures to occur.
 Unlike addition polymerization, step-wise reactions involve
two different types of di-functional monomers or end
groups that react .with one another, forming a chain
 Condensation polymerization also produces a small
molecular by-product (water, HCl, etc.).
 Cont’d

 Below is an example of the formation of Nylon 66, a

common polymeric clothing material, involving one each of
two monomers, hexamethylene diamine and adipic acid,
reacting to form a dimer of Nylon 66.
H H O O
N (CH2 ) N + C (CH )
6 2 4 C
H Hexamethylene H HO HO
diamine Adipic acid
(This polymer is known as H O
nylon 66 because of the six H O
carbon atoms in both the N (CH2 )6 N C (CH )4
hexamethylene diamine 2 C + H2 O
and the adipic acid.) H Hexamethylene adipamide HO water
(Nylon 66)
 Cont’d

 At this point, the polymer could grow in either direction by

bonding to another molecule of hexamethylene diamine or
adipic acid, or to another dimer.
 As the chain grows, the short chain molecules are called
oligomers.
 This reaction process can, theoretically, continue until no
further monomers and reactive end groups are available.
 Cont’d

The process, however, is relatively slow and can take

up to several hours or days.
Typically this process breeds linear chains that are
strung out without any cross-linking or branching,
unless a tri-functional monomer is added.
It is not unusual for branches or cross-links with
other chains to occur along the main chain in
addition polymerisation, in contrast.
Polymer classification based on their molecular structure
 The monomers in a polymer can be arranged in a number of
different ways: Linear, Branched and Cross-linking .
 Linear polymers are made up of one long continuous chain,
without any excess appendages or attachments
 Branched polymers have a chain structure that consists of one
main chain of molecules with smaller molecular chains branching
from it
 Cross-linking in polymers occurs when primary valence
bonds are formed between separate polymer chain molecules
 Cont’d
 Homopolymers:-Chains with only one type of monomer
 Copolymer:- defined as polymeric materials containing two
or more kinds of monomers which can have different
arrangements of the monomers along the chain:

Random Copolymers: Alternating Copolymers: Block Copolymers: Graft Copolymers:

Different monomers Different monomers Different monomers Appendages of one
are randomly arranged show a definite are arranged in long type of monomer are
within the polymer ordered alternation. blocks of each monomer. grafted to a long chain
chains. of the other.
 Polymer properties
Polymers have three main properties : Molecular
weight, Crystallinity and Glass transition temperature
(Tg).
 The molecular weight of polymers is not fixed because of
varying chain length, linear chains are flexible while
branched chain polymers are tough.
 Because of high molecular weight and varying chain length,
most polymers are amorphous and only semi-crystalline.
 Cont’d

 Those with high Crystallinity are tougher, more opaque,

more resistant to solvents, higher density and sharply
defined melting point
 At low temperature, even amorphous polymers are hard and
brittle (glass-like).
 As temperature is increased, kinetic energy increases
 At a certain temperature called the glass transition
temperature, a polymer loses glass-like properties and
becomes softer and more elastomeric but it does not melt
 Polymer Physical Structure
 Segments of polymer molecules can exist in two distinct
physical structures: either crystalline or amorphous forms.
 Crystalline polymers are only possible if there is a regular
chemical structure (e.g., homopolymers or alternating
copolymers), and the chains possess a highly ordered
arrangement of their segments.
 Semi-crystalline polymers possess a rather typical
liquefaction pathway, retaining their solid state until they
reach their melting point at Tm.
 Cont’d

 Amorphous polymers do not show order

 The molecular segments in amorphous polymers or the
amorphous domains of semi-crystalline polymers are
randomly arranged and entangled.
 At low temperatures, below their glass transition
temperature (Tg), the segments are immobile and the sample
is often brittle.
 As temperatures increase close to Tg, the molecular
segments can begin to move.
 Cont’d
 Above Tg, the mobility is sufficient (if no crystals are
present) that the polymer can flow as a highly viscous
liquid.
 The viscosity decreases with increasing temperature and
decreasing molecular weight.
 There can also be an elastic response if the entanglements
cannot align at the rate a force is applied (as in silly putty),
material is then described as visco-elastic.
 Cont’d
 In a semi-crystalline polymer, molecular flow is prevented
by the portions of the molecules in the crystals until the
temperature is above Tm, at this point a visco-elastic
material forms.
 These effects can most easily be seen on a specific volume
versus temperature graph.
 Figure :Specific Volume versus Temperature graph

Viscous

liquid
In the fig. between Tg

Amorphous and Tm, the semi-crystalline

solid shrinkage due polymer is a tough solid. The

specific

to freezing amorphous material changes to a

volume

viscous liquid after Tg. This is

when the material can be easily

deformed.

semi-crystalline
T T
g solid
m

temperature
 Plastics
 A plastic is a material that contains as an essential
ingredient, an organic substance of a large molecular
weight, is solid in its finished state, and, at some stage in its
manufacture or in its processing into finished articles, can
be shaped by flow.
 In practice, a plastic is usually considered to be an
amorphous or crystalline polymer which is hard and
brittle at ordinary temperatures
 Cont’d
 Polymers can be separated into two different groups
depending on their behavior when heated: thermoplastic &
thermosets.
 Thermoplastics:-substances that soften upon heating and
can be remolded and recycled which can be semi-crystalline
or amorphous.
 Thermoplastics are generally carbon containing polymers
synthesized by addition or condensation polymerization.
 Cont’d

 Polymerization process forms strong covalent bonds within

the chains and weaker secondary Van der Waals bonds
between the chains.
 Usually, these secondary forces can be easily overcome by
thermal energy, making thermoplastics moldable at high
temperatures.
 Uses of various thermoplastic materials
Plastic type Uses

Nylon (nylon-6,6 & nylon-6) a substitute for silk for making parachutes,
vehicle tires, garments and many other
products, fabrics, footwear, fishnets and
carpets
Low density polyethylene (LDPE) Packaging films, wire and cable insulation,
toys, flexible bottles, houseware

High density polyethylene (HDPE) Bottles, drums, pipes, films, sheets, wire and
cable insulation

Polypropylene PP Automobile and appliances parts, furniture,

cordage, carpets, film packaging

Polyvinyl chloride PVC Construction, rigid pipes, flooring, wire and

cable insulation, film and sheet

Polystyrene Packaging (foam and film), foam, insulation,

insulation, appliances, houseware
 Thermosets
 Substances that do not soften under heat and pressure and
cannot be remolded or recycled.
 They must be remachined, used as fillers, or incinerated to
remove them from the environment.
 Strong covalent bonds chemically hold different chains
together in a thermosets material.
 The chains may be directly bonded to each other or be
bonded through other molecules.
 Cont’d

 This "cross-linking" between the chains allows the material

to resist softening upon heating.

 Although thermosets are difficult to reform, they have
many distinct advantages in engineering design applications
including: High thermal stability and insulating properties,
High rigidity and dimensional stability, Resistance to creep
and deformation under load, Light-weight.
 Cont’d

 Thermosetting plastics (thermosets) are polymer materials

that cure or are made strong by addition of elements (e.g.
sulphur) or addition of energy in form of heat (normally

above 200oC) through some chemical reaction.

 Before curing process, they are usually in liquid form,
powder or malleable forms that can be moulded to a final
form or used as adhesives.
 Cont’d
 The curing process transforms these materials into plastic or
rubber through a cross linking process.
 The cross links produce a three dimensional rigid structure
of the material with large molecular weight and a high
melting point.
 Examples of thermosets include: polyester resin,
vulcanized rubber, Bakelite and epoxy resin.
 Uses of Principal thermosetting plastics
Thermosetting plastic Uses

Phenol-formaldehyde (PF) Electrical and electronic equipment,

automobile parts, utensils, handles, plywood
adhesives, particle board binder

Urea-formaldehyde (UF) Similar to PF, textile treatment, coating

Unsaturated polyester (UP) Construction, automobile parts, marine

accessories

Epoxy Protective coating, adhesives, electrical and

electronics, industrial flooring, material
composites

Melamine-formaldehyde (MF) Similar to UF, decorative panels, counter and

table tops, dinnerware
 Polyethylene
There are three major classes of polyethylene:
low density polyethylene (LDPE),
high density polyethylene (HDPE) and
linear low density polyethylene (LLDPE)
 Pellets of these plastics are extruded and blown to produce
film.
 This film is used for packaging and making plastic bags.
 Cont’d

 Ethylene is derived from either modifying natural gas (a

methane, ethane, propane mix) or from the catalytic
cracking of crude oil.
 In a highly purified form, it is piped directly from the
refinery to a separate polymerization plant.
 Under the right conditions of temperature, pressure and
catalysis, the double bond of the ethylene monomer opens
up and many monomers link up to form polyethylene.
 Cont’d
 In commercial polyethylene, the number of monomer repeat
units ranges from 1000 to 10 000.
 Molecular weight ranges from 28,000 to 280,000.
 Polyethylene Manufacturing Process

 Today, polyethylene manufacturing processes are usually

categorized into "high pressure" and "low pressure"
operations.
 High pressure:- producing low density polyethylene
(LDPE)
 Low pressure:- makes high density (HDPE) and linear low
density (LLDPE) polyethylenes.
 Cont’d

 The polymerization reaction which occurs is a random one,

producing a wide distribution of molecule sizes.
 By controlling the reaction conditions, it is possible to
select the average molecule size (or molecule weight) and
the distribution of sizes around this average (molecular
weight distribution).
 The chains are highly branched (at intervals of 20 – 50
carbons).
 Cont’d

 The most common method used in industry is to polymerize

ethylene by means of a fluidized reactor bed.
 A fluidized reactor bed consists of metallic catalyst particles
that are 'fluidized' by the flow of ethylene gas.
 This means that the catalyst particles are suspended in the
ethylene fluid as ethylene gas is pumped from the bottom of
the reactor bed to the top.
 Polyethylene comes out of the reactor as granular powder,
which is then melted and flows through a film extruder.
 High pressure process for the manufacture of polyethylene
(LDPE) `

Catalyst High Low

Reactor pressure pressure
Separator separator

Secondary
compressor
Extruder /
Pelletizer
Primary
compressor
High purity ethylene Polyethylene pellets
 Low pressure process for manufacture of HDPE
recycled ethylene

Compressor Compressor

granular polyethylene
Fluid bed
Separator Extruder
Ethylenereactor
Catalyst Polyethylene pellets
 Cont’d

 Whatever the type of polyethylene produced, the end

product is usually available in the form of small pellets,
varying in shape (spherical, rectangular, cylindrical)
depending upon the manufacturer's equipment.
 During the manufacture of polythene products, it is melted

to flow through a film extruder.

 Polyvinylchloride (PVC)
 Polyvinylchloride (PVC) [-(-CH2 -CHCl-)n-] is one of the

three most important polymers currently used worldwide.

 This is because PVC is one of the cheapest polymers to
make and has a large range of properties so can be used to
make hundreds of products.
 PVC is formed by the polymerization of vinyl chloride
(chloromethane) monomer units:
 Cont’d

PVC consists of polar molecules which are attracted to each

other by dipole-dipole interactions due to electrostatic
attractions of a chlorine atom in one molecule to a hydrogen
atom in another atom.
 Cont’d

These considerable intermolecular attractions between

polymer chains make PVC a fairly strong material.
Uncompounded PVC is colorless and rigid and possesses
poor stability towards heat and light
 Cont’d

 However, the use of additives/stabilizers enables us to

change the properties of the PVC to how we desire.
 The blender: Additives are blended with PVC to determine
the properties of the PVC we want to form.
 The relevant additives are mixed with the polymer in a
process called compounding.
 blends all the ingredients using an intensive high-speed
mixer to form a 'dry blend' powder, which is then fed into
the processing equipment or
 Cont’d

 blends the ingredients in either a high or low speed mixer

and then the powder is transferred to a melt compounder.
 This produces a melt which, when cool, is cut into granules
ready for processing.
 A variety of processing methods such as extrusion, injection
moulding, blow moulding and coating are then applied to
the PVC compounds to form products.
 Cont’d
• plasticizers (make products flexible)
• heat stabilizers (prevent PVC decomposing when heated)
• lubricants (control its rate of flow when it is molten and
prevents it from sticking to metal surfaces)
• processing aids and impact modifiers (make plastic more
workable or make the final article stronger)
• fillers (make up half the weight of a PVC plastic article to
increase profits)
 Cont’d

• colourants (organic dyes or inorganic pigments)

• flame retardants (PVC is less flammable than most
polymers but by adding a few % antimony oxide makes it
even less so)
• Other specialist additives are antistatic agents, biostabilisers
and viscosity modifiers.
 PVC manufacture

 The manufacture of PVC accounts for 30% of the chlorine

produced industrially.
 Ethylene comes from oil or natural gas which is refined and
'cracked' by heating ethane, propane or butane or naphtha
from oil.
 Pressure is applied to vinyl chloride (dispersed in water as a
suspension or an emulsion) in high pressure chambers at
temperatures of 50-70°C.
 Cont’d

 The role of water is to remove and control the heat given off
in the polymerisation process.
 PVC forms as tiny particles which grow and when they
reach a desired size the reaction is stopped and any
unreacted vinyl chloride is distilled off and re-used.
 The PVC is separated off and dried to form a white powder.
 Phenol-formaldehyde resins

 Bakelite is a thermosetting resin that is once molded it

retains its shape even if heated or subjected to various
solvents.
 Bakelite is the condensation polymerization product of
phenol and formaldehyde in the presence of an acid or base
catalyst.
 Cont’d

 The nature of the product formed depends upon two factors:

(i) the proportion of the reactants (phenol and formaldehyde)

and
(ii) the nature of the catalyst (acidic or basic)
Cont’d
 Natural and synthetic Rubbers
 Synthetic rubbers (elastomers) are long-chain polymers
with special chemical and physical as well as mechanical
properties.
 These materials have chemical stability, high abrasion
resistance, strength, and good dimensional stability
 Many of these properties are imparted to the original
polymer through cross linking agents and additives.
 Cont’d
 An important property of elastomeric materials is their
ability to be stretched at least twice their original length and

to return back to nearly their original length when released .

Natural rubber is an elastomer constituted of

isoprene units.
 These units are linked in a cis-1,4 configuration that gives
natural rubber the outstanding properties of high resilience

and strength.
 Cont’d

 Vulcanization of rubber is a chemical reaction by which

elastomer chains are linked together.
 The long chain molecules impart elasticity, and the cross
links give load supporting strength.
 The major use of rubber is for tire production.
 Non-tire consumption includes hoses, footwear, molded
and extruded materials, and plasticizers.
 Cont’d
 An elastomer (or rubber) is a word having its origin from
two words: “elastic” which means the ability to return to
original shape when a force or stress is removed and “mero”
which means “parts“ implying many parts or monomers.
 Therefore, an essential requirement of an elastomer is that it
must be elastic i.e. it must stretch rapidly under tension to
several times its original length with little loss of energy as
heat.
 Cont’d
 Industrial elastomers have high tensile strength and high
modulus of elasticity.
 They are amorphous polymers with considerable cross-
linkages.
 The covalent cross-linkages make the elastomer to return to
its original structure or shape when the stress is removed.
 Without cross-linkages or with short chains, the applied
force would result in a permanent deformation.
 Cont’d
 They are usually thermosets that require vulcanization, but
there are some which are thermoplastic.
 Elastomers include:

Nitrile rubber, Butyl rubber, Silicone rubber, Polyurethane

rubber, Polysulphide rubber, Polybutadiene, Styrene-
butadiene, Polyisoprene, Tetrafluoroethylene,
Tetrafluoropropylene etc
 Cont’d
 Styrene-butadiene rubber (SBR) is the most widely used
synthetic rubber.
 It can be produced by the copolymerization of butadiene (≈
75%) and styrene (≈ 25%) using free radical initiators.
 Emulsion polymerized styrene-butadiene rubber (E-SBR)
is one of the most widely used polymers in the world today.
 Emulsion SBR is employed in many demanding
applications, which enhance the quality of life and
contribute significantly to our economy and standards of
 Cont’d

 SBR is widely used for rubber belting, hose, flooring,

molded goods, rubber soles, coated fabrics etc.
 It is compatible with natural rubber and has equal
performance for automobile tyres.
 But it is inferior to natural rubber for heavy duty truck
tyres.
 Polyisoprene

 Isoprene can be polymerized using free radical initiators,

but a random polymer is obtained.
 As with butadiene, polymerization of isoprene can produce
a mixture of isomers.
 However, because the isoprene molecule is asymmetrical,
the addition can occur in 1,2-, 1,4- and 3,4- positions.
 Six tactic forms are possible from both 1,2- and 3,4-
addition and two geometrical isomers from 1,4- addition
(cis and trans):
 Cont’d

Stereo regular polyisoprene is obtained when Ziegler-

Natta catalysts or anionic initiators are used.
The most important coordination catalyst is α- TiCl3

cocatalyzed with aluminum alkyls.

 Natural and synthetic Fibers

 Fibers are solid materials characterized by a high ratio of

length to diameter.
 They can be manufactured from a natural origin such as silk,
wool, and cotton, or derived from a natural fiber such as
rayon.
 They may also be synthesized from certain monomers by
polymerization (synthetic fibers).
 In general, polymers with high melting points, high
crystallinity, and moderate thermal stability and tensile
 Cont’d

 Animal fibers, such as wool or silk and vegetable fibers,

such as cotton, continue to be used although there is a
wealth of synthetic fibres such as cellulose acetate and
nylon, acrylic and polyester.
 Carbon fibres for making advanced composites are
produced by heat treatment of polyacrylonitrile and other
synthetic fibres.
 Cont’d

 Man-made fibers include, in addition to synthetic fibers,

those derived from cellulose (cotton, wood) but modified by
chemical treatment such as rayon, cellophane, and cellulose
acetate.
 These are sometimes termed “regenerated cellulose fibers.”
 Rayon and cellophane have shorter chains than the original
cellulose due to degradation by alkaline treatment.
 Polyester fibers

 Polyesters can be produced by an esterification of a

dicarboxylic acid and a diol, a trans-esterification of an
ester of a dicarboxylic acid and a diol, or by the reaction
between an acid dichloride and a diol.
 The polymerization reaction could be generally represented
by the esterification of a dicarboxylic acid and a diol as:
 Cont’d
 Polyethylene terephthalate (PET) is produced by esterifying
terephthalic acid (TPA) and ethylene glycol or, more commonly,
by the trans-esterification of dimethyl terephthalate and ethylene
glycol.

 This route is favored because the free acid is not soluble in many

organic solvents.
 Reaction occurs in two stages;

 Methanol is released in the first stage at approximately 200°C

with the formation of bis(2-hydroxyethyl) terephthalate.

 Cont’d
 In the second stage, polycondensation occurs, and excess
ethylene glycol is driven away at approximately 280°C and
at lower pressures.
 Polyamide fibers

 Polyamides are the second largest group of synthetic fibers

after polyesters.
 Polyamides are produced by the reaction between a
dicarboxylic acid and a diamine (e.g., nylon 66), ring
openings of a lactam, (e.g., nylon 6).
 Nylon 66 is produced by the reaction of
hexamethylenediamine and adipic acid monomers.
 This produces hexamethylenediammonium adipate salt.
 Cont’d

 The product is a dilute salt solution concentrated to

approximately 60% and charged with acetic acid to a
reactor where water is continuously removed.
 The presence of a small amount of acetic acid limits the
degree of polymerization to the desired level.