Polymers

An Introduction to Polymer Chemistry

 Introduction

• Polymer (Greek: poly=many; mer=part)

giant, complex molecules
• Made up by the linking together of large number of
small molecules (repeating units called monomers )
held together by covalent bonds (two or more bonding
sites)
 Monomers
Alkenes, vinyl chloride, adipic acid, glucose, amino acids, glycol
with two bonding sites act as monomers

H H

C C

H H

E thylen e
Isoprene

adipic acid

terephthalic acid

hexane-1,6-diamine

ethane-1,2-diol Aminoacid
 Polymerization
Monomer Polymer

MW 28 MW 28000

Butadiene, MW 54 Polybutadiene, MW 200000

 Degree of Polymerization
• Number of repeating units in the polymer chain
formed is called the degree of polymerization
(n).
• Polyethene: (C2H4) n, where n stands for DP
• Molecular weight of PE, M = nMo,
where Mo is molecular weight of monomer
• Strength of the polymer can be increased by
increasing its DP
– High DP hard and heat resistant
– Low DP soft, gummy
 Degree of Polymerization
• Data: If MW of PE, M = 28000,
MW of repeat unit, Mo = 28,
M = nMo
• Thus, n = M/Mo
= 28000/28
= 1000
Degree of Polymerization (n) = 1000
 Classification
i) On the basis of origin
– Natural
– Synthetic
ii) On the basis of nature of monomer
• Homopolymers (comprise of monomers of the same type)
– Linear (homochain or heterochain)
– Branched
– Cross-linked
• Heteropolymers/ Copolymers (Different repeating units)
– Linear; Branched; Graft (regular/irregular); Block
(regular/irregular)
iii) On the basis of chemical nature
• Organic (polymer backbone chain made up of carbon atom)
• Inorganic (No carbon atoms in the backbone chain, eg., Silicone
rubbers)
 Nomenclature
Homopolymers can be linear,
branched or cross-linked
Homopolymer: Monomers of the

Copolymer: Different repeating units

Random copolymer: Two or more different repeating units are

Alternating copolymer: Alternating sequences of different monomers

Block copolymer: Long sequences of a monomer are followed by long

sequences of another monomer
Graft copolymer: Chain made from one type of monomer
with branches of another type
 Tacticity:
Tacticity: Orientation of monomeric units in polymer takes
place in orderly/disorderly fashion w.r.t main chain.
The difference in configuration affects their physical
properties
Isotactic: Head-to-tail configuration
Functional groups are all on the same side of the main
chain, FG= Y
 Tacticity:
Syndiotactic: Functional groups occupy alternating position.

Atactic: Functional groups arranged in random manner

For example, atactic polypropylene is a gummy solid, while

isotactic version is highly crystalline & tough.
 Types of Polymerization
• Polymerization
Fundamental process in which low molecular weight
compounds combine to form giant molecules/
macromolecules of high molecular weight

Three types of polymerization

• Addition
• Condensation
• Copolymerization
 Addition Polymerization
• formed from the monomer, without the loss of any
byproduct, like small molecules. Monomers with
double or triple bonds tend to polymerize without the
liberation of small molecules. Example: Polyethylene
(PE)
• It yields product that is an exact multiple of the original
monomer unit
 Common Polyolefins
Monomer Polymer
CH3
H3C
Polyethylene n
Repeat unit
Ethylene

CH3
CH3 n
Polypropylene CH3 CH3 CH3 CH3 CH3 CH3 CH3
Propylene

CH3
Ph n
Polystyrene Ph Ph Ph Ph Ph Ph Ph
Styrene

CH3
Cl n
Poly(vinyl chloride) Cl Cl Cl Cl Cl Cl Cl
Vinyl Chloride
F2 F2 F2 F2 F2 F
F2C CF2 C C C C C 2 CF3
FC C C C C
nF
C C C
Tetrafluoroethylene 3
Poly(tetrafluoroethylene): Teflon F F F 2 F F
2 2 2 2 2
 Condensation/Step Polymerization
• Formation of polymers from polyfunctional monomers
of organic molecules with elimination of small
molecules like water, HCl
• Functional group of one monomer unit reacts with
functional group of the other
• Eg- Nylon-66 (hexamethylene diamine + adipic acid)
 Polyesters & Amides

Monomer Polymer
O O
H2 H2
HO2C CO2H OH HO O C C O H
HO
Ethylene Poly(ethylene terephthalate n
Terephthalic
acid glycol Ester

O O O O
H
HO 4
OH H2N 4
NH2 HO N 4 N
4
Adipic Acid 1,6-Diaminohexane Nylon 6,6 H H n
Amide
O O
H H
HO2C CO2H H2N NH2 HO N N H
Kevlar n
Terephthalic 1,4-Diamino
acid benzene
 Natural Polymers
Monomer Polymer

Isoprene Polyisoprene:
Natural rubber n
H OH H OH
HO H HO
HO O
HO OH HO OH
H OH Poly(ß-D-glycoside): H OH
H H cellulose H H n
ß-D-glucose
O O O O
H H
H3N H3N N N OH
O Polyamino acid: R1 Rn+1 Rn+2
n
R protein
Amino Acid
O O
DNA
O P O Base O P O
O Base
O O O
oligonucleic acid
OH DNA
O
Nucleotide DNA
Base = C, G, T, A
 Copolymerization
• Specific type of addition polymerization, without loss
of any small molecules
• Monomers of more than one type are involved thereby
giving variety of polymers
• Eg. Styrene-Butadiene rubber (Buna-S)
 Mechanism
• Initiation: Free radicals formed from H2O2 through
the addition of heat

Free radical acts to open the C=C double bond by joining to one
side of the monomer.
This allows the monomers to react with other open monomers on
their other side.
 Mechanism
• Propagation: Process continues with successive addition of
monomer units to the chains

• Termination: Once the desired polymer is obtained, the

polymerization reaction is terminated by combining two
chains
 Polymer Crystallinity

• Polymers are never completely crystalline crystalline

regions with amorphous regions are together
• Polymer is crystalline if all molecules are arranged in an
orderly manner with symmetrical orientation
• Degree of crystallinity depends on DP & tacticity
• Crystalline polymers possess high density, sharp melting
points, strong, brittle and hard
• Amorphous polymers do not possess melting points,
but softening points
 Melting and Glass transition temperatures

• Lowest temperature beyond which polymer becomes

hard, brittle, glass-like or temperature at which polymer
experiences transition from rubbery to rigid states is
called glass transition temperature (Tg)
In this state, solid tends to shatter if it is hit, since the
molecular chains cannot move easily.
• Temperature above which polymer turns out to be
flexible, elastic and rubbery (Tm)
 Effect of heat on polymer
Beyond glass transition temperature, crystalline and amorphous
polymer behaves differently as shown in the diagram below.
 Significance

• Tg and Tm are significant parameters

• Gives an indication of the temperature region at which
a polymeric material transforms from a rigid solid to a
soft viscous state
• Helps in choosing the right processing temperature in
which materials are converted into finished products
 Factors affecting Tg

• Tg is directly proportional to the molecular

weight of the polymer.
• Greater the degree of cross-linking, higher the Tg.
• Polymers with strong intermolecular forces of
attraction have greater Tg.
• Side groups, especially benzene and aromatic
groups attached to main chain increases Tg.
 Molecular Weight
Number average Molecular weight
• Consider a polymer sample in which n1, n2 and n3… are number
of molecules with molecular weights M1 ,M2 ,M3 …respectively
then,

Where, ni is number of molecules of mass Mi

 The number average molecular weight
Total Mass of Each Type of
Number of Molecules, Ni Mass of Each Molecule, Mi Molecule, NiMi
1 800,000 800,000

3 750,000 2,250,000
5 700,000 3,500,000
8 650,000 5,200,000
10 600,000 6,000,000
13 550,000 7,150,000

20 500,000 10,000,000
13 450,000 5,850,000
10 400,000 4,000,000
8 350,000 2,800,000
5 300,000 1,500,000
3 250,000 750,000
1 200,000 200,000
Ni = 100 Total Mass = NiMi = 50,000,000

NiMi, where Ni is the number of molecules of weight M

i
The number average molecular weight for this sample is then,
NiMi / Ni = 50,000,000/100 = 500,000
 Weight Average Molecular Weight
• If m1 , m2 , m3 … are masses of the species with molecular weights
M1,M2, M3… resp. (m 1=n 1M 1 where, n 1 is number of molecules
with molecular weight M1)

=
But, mi=niMi

(mi=nM
i i where, n i is number of molecules with molecular weight Mi )
 Average molecular weight
Total Mass of Weight Fraction
Number of Mass of Each
Each (Wi)
Molecules Molecule
Type of Molecule Type of Molecule

(N)i (M)i (NM)

i i (NM/
i i N iM i) (W M )
i i
1 800,000 800,000 0.016 12,800
3 750,000 2,250,000 0.045 33,750
5 700,000 3,500,000 0.070 49,000
8 650,000 5,200,000 0.104 67,600
10 600,000 6,000,000 0.120 72,000
13 550,000 7,150,000 0.143 78,650
20 500,000 10,000,000 0.200 100,000
13 450,000 5,850,000 0.117 52,650
10 400,000 4,000,000 0.080 32,000
8 350,000 2,800,000 0.056 19,600
5 300,000 1,500,000 0.030 9,000
3 250,000 750,000 0.015 3,750
1 200,000 200,000 0.004 800
Weight Average Molecular Weight W M = 531,600
i i

The distribution of molecular weights in a polymer sample is often described by the ratio of the
weight average molecular weight to the number average molecular weight. In this case the ratio is
531,600/500,000 = 1.063. This ratio is the Polydispersity Index (or PDI).
 • Viscosity Average Molecular weight

Where, ni is the number of individual molecules having

the molecular mass Mi .
Exponent a, between 0.6 and 0.8 for many
polymer/solvent systems
 Rubber
• In 1953, Hermann Staudinger formulated
a macromolecular structure for rubber
and received the Nobel Prize.
based on the repeating unit
2-methylbuta-1,3-diene

isoprene
 Elastomers/ Rubbers
• The polymers possessing elasticity to the extent of
nearly 200 to 300 percent are known as Elastomers
or Rubber
• Amorphous polymer with numerous cross linkages
and high degree of elasticity deformed by
stretching & regain original form when stretching
force is removed
r e le a s e o f
A p p lied B a c k to
U n str e ssed R u b b er S tr esse d R u b b e r
str ess S tress o r ig in a l p o sitio n

• Rubber has no crystallinity. Their extension and contraction are

due to temporary movements of segments of polymer chain.
The chains do not slip past each other due to cross linkages
 Properties of Rubber

Important properties of rubber are its

• Flexibility
• Strength
• Impermeability to water
• High resistance to abrasion etc,

Due to these properties rubber is highly useful for industrial as well

as domestic purposes.
 Types of Rubber

1. Natural Rubber- Obtained from natural sources

1. Synthetic Rubber- Made synthetically

 Natural Rubber
• Raw material from rubber tree (Hevea
brasiliensis) is tapped every second day for its
sap, known as latex, by making slanting cuts in
the bark of the tree.
• Latex is collected and acetic acid is added to it so
as to precipitate out the rubber, which then
hardens/coagulates.
• After being washed and dried, rubber is cured in
special smokehouses to protect it against
microbial attack.
• Purer the rubber, higher the grade – it is ready
for delivery to rubber companies worldwide.
 • Natural Rubber
• Polymer of isoprene (2-methyl-1,3-butadiene)
• Low tensile strength, elasticity over a narrow
range of temperature

Isoprene
Rubber +
Destructive
distillation Dipentene

indicates number of isoprene units.

Molecular weight of rubber is very high of about 300,000.
 Structure of Rubber
Rubber which is composed of all cis-linked isoprene units,
forms an amorphous structure that is highly elastic. On the
other hand, gutta percha, which is a polyisoprene compound
made of all trans-linked isoprene units, forms linear strands
which can interact into crystalline arrays that have plastic
properties, but are not elastic.
 Drawbacks of Natural rubber

• Its plasticity is greater than elasticity. It can’t

sustain stress. Thus when stretched to a great
extent, it undergoes deformation permanently.
• It has large water absorption tendency, which
make it week
• Limitations of natural rubber: It softens at high
temperature and becomes brittle at low
temperature.
• Natural rubber is attacked by acids, oxidizing
agents, non-polar solvents and oxidized by air.
To overcome these limitations rubber is
vulcanized.
 Vulcanization
• Vulcanization is a process which is essentially
compounding rubber with different chemicals like
sulphur, H2S, benzoyl chloride etc.

• Heating raw rubber with sulphur at 100 -140 ˚C.

Sulphur enters the double bonds of rubber and forms
cross-linkages. Excellent changes in properties,
resistance to changes in temperature, increased
elasticity, tensile strength, durability, chemical resistance

• Brings about stiffening of rubber by anchoring &

restricting intermolecular movement by providing
cross-linkages between chains.
Vulcanization
• The toughness or stiffness of vulcanization
depends on the amount of sulphur included.
• For flexible tyre rubber, sulphur content is
from 3-5% whereas for tougher variety like
ebonite, content of sulphur is 32 %.

• Ebonite is so tough that it can be machined

and has very good electrical insulation property.
Property Raw Rubber Vulcanized Rubber
Elasticity Very high Low, depending on % S
Tensile Strength 200 kg/cm2 2000 kg/cm2
Chemical resistance Very poor Higher
Durability Less Higher
Quality Inherent Can be controlled by
vulcanization
 Applications of rubber

• Due to remarkable resistance to electricity, it is used as

an insulating coating on wires and cables, used for
electric power transmission.
• Due to its elasticity, it is used to fabricate rubber bands,
rubber goods, golf balls, tubes for automobiles, etc
• It acts as an excellent adhesive
• Foam-rubber is used for making pillows, cushions,
mattresses, automotive pads, etc.
• Polysulfide rubber is used as a solid-propellant fuel for
rocket motors.
Preparation, Properties and Uses of
Commercial Rubbers
 Buna-S Rubber/Cold Rubber
Synthetic rubber is any vulcanizable man-made rubber-like polymer
which can be stretched to twice its length and on releasing the stress, it
returns to its original shape and size.

Copolymerization of butadiene & styrene carried out at 5oC

Good and tough mechanical properties
Easily attacked by oxidizing agents, mainly ozone, organic solvents
Uses: Manufacture of tyres, insulating wires and cables, adhesives,
lining of vessels
 Polyurethane (Isocynate) Rubber

• Ethylene glycol polymerizes with ethylene diisocyanate to form

polyurethane rubber.
• Highly resistant to oxidation
• Resistant to organic solvents, attacked by acids and alkali
Uses: surface coatings and manufacture of foams and fibers
 Industrial Polymers

The world consumption of synthetic polymers

: 150 million metric tons per year.

1) Plastics : 56%
2) Fibers : 18%
3) Synthetic rubber : 11%
4) Coating and Adhesives : 15%
 Plastics
The polymeric materials, which are rigid, dimensionally
stable and usually brittle are known as plastic.

ThermoPlastics/Thermosoftening Polymers
• Some polymers when heated become soft and can be
moulded into any shape that can retain on cooling
• PVC, PE, nylon sealing wax, etc
Thermosetting polymers
• On heating, polymers undergo a chemical change and
become an infusible mass which cannot be reshaped
• Bakelite, polyester, resins
 Comparisons
Thermoplastic polymers Thermosetting polymers
They soften on heating and harden on They are fusible on initial heating, but
cooling turn into hard infusible mass on heating
further
Can be reshaped and recycled Cannot be reshaped and recycled
Formed by addition polymerization Formed by condensation polymerization
Linear in structure Three dimensional in structure
They are soluble in some organic solvents Insoluble in organic solvents
Moulded articles are taken out after cooling Moulded articles are taken out from the
the mould to avoid deformation of the mould even when they are hot.
article
e.g. Polyethylene, polystyrene, PVC, PVA e.g. Nylon 6:6, Phenolformaldehyde,
ureaformaldehyde,
 Compounding of Plastics

• Unusual for a finished high polymeric articles to solely

consist of high polymers alone
• Mixed with ingredients known as additives resulting in
useful functions and imparts useful properties to the
finished products
• Main types of compounding ingredients are
– Resin: Binder, which holds different constituents/additives
together. Natural or synthetic resins used in this case
• Plasticizers: Low MW organic liquids added to polymer to
improve its flexibility; Added 8-10% of total bulk of plastics
(oils, camphor, dioctyl phthalates) The small molecules penetrate
into the polymer matrix and neutralize a part of intermolecular
forces of attraction between macromolecules and increase
mobility of polymer segments so that chains can slide over each
other. Hence, plasticizers act as an internal lubricant
• Stabilizers: Most polymers do not possess chemical
stability change colors & decompose
– Stabilizers are additives which chemically stabilize the polymer
and thus arrest degradation
– Organic, inorganic, organometallic compounds like CaO, BaO,
Organo-tin compounds
• Fillers/Extenders: Inert material added to enhance
mechanical strength-- asbestos powder, saw dust, cotton
pulp, clay, etc
• Lubricants: Glossy finish to product, Prevents plastics
from sticking to fabrication equipments; oils, waxes,
soaps, etc
• Catalysts
Antioxidants like H 2O 2, benzoyl peroxide, ZnO, NH 3,
Ag, Pb, are added to the polymeric matrix to accelerate
the cross linking in thermosetting plastics while
moulding process
• Coloring materials
Organic dyes and pigments impart desired color for
aesthetic appeal of the finished polymeric material.
Some colors are added to impart UV protection to the
finished products.
Preparation, Properties and Uses of
Commercial Plastics
 Phenol Formaldehyde Resin

Acid or a base as a catalyst to undergo condensation polymerization

product nature depends on the catalyst and ratio of phenol and formaldehy
Novolac resin is a linear thermoplastic polymer, whereas
Bakelite is a cross-linked thermosetting polymer.
 Properties and Uses
• Phenolic resins are rigid, hard, water resistant
• Resistant to acids, salts, organic solvents
• Easily attacked by alkalies due to the presence of free
hydroxy groups
• Possess electrical insulating properties due to low
thermal conductivity
• Uses:
– Used to fabricate insulators, plugs, switches
– Used as cation-exchanger resin in water softening
– Adhesives in paints and varnishes
– Propellar shafts for paper industry and mills
 Poly(methyl methacrylate) (PMMA)
• Poly(methyl methacrylate) (PMMA) is a transparent
thermoplastic often used as a lightweight or shatter-
resistant alternative to glass.
• Although it is not technically a type of glass, the
substance has sometimes historically been called acrylic
glass.
• Chemically, it is the synthetic polymer of methyl
methacrylate.
Property
 Applications of PMMA
. Safety glass such as Plexiglass and Lucite – uses
range from windows for aquariums and under-
water restaurants to safety shields at hockey
rinks to skylights in your home to simple
paperweights
. Used as bone cement for use in arthroplastic
procedures of the hip, knee, and other joints for
the fixation of polymer or metallic prosthetic
implants to living bone
. Used in Pacemakers
. Artificial eye lenses used for cataract surgery
 Urea formaldehyde resin

Monomethylol urea on polymerization, yields a linear UF resin polymer

• Urea-formaldehyde resin yields clear, water-white
products.
• Hardness, tensile strength is comparatively better than
phenolic resins
• Better heat & moisture resistance
Uses:
• Adhesives for plywood, decorative laminates- surface
coatings
• Due to their colorability, solvent, grease resistance
cosmetic containers
• Electrical insulation
 Conducting Polymers

• Polymers are poor conductors of electricity, due to non-

availability of large number of free electrons
• The polymeric material which possess electrical
conductivities on par with metallic conductors known as
conducting polymer.
• Polymers with polyconjugated structures are insulators in
pure state, but when treated with oxidizing or reducing
agents can be converted into polymer salts with electrical
conductivities comparable to metals.
 What makes the material conductive?

Diamond, which contains only σ bonds, is an insulator and its

high symmetry gives it isotropic properties.
Graphite and acetylene both have mobile π electrons and are,
when doped, highly anisotropic metallic conductors.
 Types of conducting polymers

Conducting polymers are classified as

• π-electron conducting polymers: In these polymers, backbone of the
polymer is made up of molecules that contain conjugated π-electrons which
extend the entire polymer and make the polymer conducting.
• Conducting element-filled polymer: Here, polymer acts as a binder that
binds the conducting elements like carbon black, metal oxides, metallic fibres
that conduct electricity.
• Inorganic polymer: A metal atom with polydentate ligand, which is a charge
transfer complex is bound to the polymer to make it conducting.
• Doped- conducting polymer: Polymer is made conducting by exposing the
surfaces to charge transfer agents in gas or in solution phase.
• Blended conducting polymer: This polymer is made by blending a
conventional polymer with a conducting polymer.
 Conditions
• Polymer should consist of alternating single and
double bonds called conjugated double bonds
• Polymer matrix has to be disturbed –
– Either by removing electrons from them (oxidation),
– Or inserting electrons into the material (reduction).
The process is known as doping
– By doping with electron donor like alkali-metal ion
or electron acceptor like AsF5, Iodine, etc polymers
turn conductive materials
 Fist conditions to become conductive:
1-The first condition for this is that the polymer consists of
alternating single and double bonds, called conjugated
double bonds.
In conjugation, the bonds between the carbon atoms are
alternately single and double. Every bond contains a
localised “sigma” (σ) bond which forms a strong chemical
bond. In addition, every double bond also contains a less
strongly localised “pi” (π) bond which is weaker.
 2nd conditions to become conductive:
2-The second condition is that the plastic has to be disturbed
- either by removing electrons from (oxidation), or
inserting them into (reduction), the material. The process is
known as Doping.
• There are two types of doping:
1-oxidation with halogen (or p-doping).
3x
CHn I CHn I3
2
x
CHn xNa CH n xNa
2- Reduction with alkali metal (called n-doping).
• Iodine molecule attracts an electron from polyacetylene chain and
becomes I3-
• Polyacetylene molecule, now positively charged, is termed a radical
cation, or polaron
• Lonely electron of the double bond, from which an electron was
removed, can move easily.
• As a consequence, double bond successively moves along the
molecule– Conducting Polymers
 Polypyrrole

•Hetero atomic polymers

•More stable
•Easy to prepare
•Greater opportunity to functionalize
Polypyrole
 Applications
Smart
Materials

Battery Conducting
Telecommunication
technology Polymers

Aerospace
 Self healing polymers
• Inspired from biological systems ‘Wound healing’
• Inherent ability of polymers to repair damage caused by
mechanical usage over time
• Terminator Polymers
• Chemistry World posted a video of the product in action,
showing someone cutting a piece of the polymer in two with a
scalpel, pressing the pieces back together and leaving it on a table
for two hours at room temperature. The person is unable to pull
the material apart with their hands upon returning.
• This is the next generation breakthrough in polymers.
• Autonomic healing: A propagating crack ruptures the
microcapsules, releasing the healing agent into the crack
plane by capillary action. Polymerization is initiated by
contact with the embedded catalyst or initiator, bonding
the crack faces, and restoring structural continuity.
• Non-autonomic healing: Partially self-
contained; healing capability is designed into the
material, but additional external stimuli such as
heat or UV-radiation is required for the healing
to occur.
 Applications
• Nissan Motor Co. Ltd has commercialized
world’s first self-healing clear coat for car
surfaces-trade name of this product is ‘Scratch
Guard Coat’
• Self healing concretes– in progress
• Self-healing materials are now used as composites
in aircrafts.
Thank you