Polymer Chemistry

Department of Applied Sciences

College of Engineering
Pune

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Contents
 Introduction  Commercially important polymers with
 Polymer Terminologies synthesis and applications
 Classification of polymers • Plastics
• Origin • Fibres
• thermal properties • Adhesives
• Constituents • elastomers
• end use  Conducting polymers-
• performance • Intrinsic and extrinsic conducting
 Properties of polymers polymers
• Solubility • Doping
• Molecular Weight • factors responsible for conduction
• Crystallinity • synthesis of a conducting polymer
• Glass transition temperature  Biodegradable Polymers
• Role of additives in polymers. • Need, Factors responsible, Features
• Synthesis
• Applications

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Introduction
 Generally organic compounds
 Very large molecular structures.
 Have low density and not stable at high temperatures.
 Can be readily formed into complex shapes.
 strength, stiffness, and melting temperatures generally much lower
than metals and ceramics.
 Preferred material for many engineering applications due to light
weight , low cost and ease of forming

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Polymer Terminologies
 Monomer
 A monomer is a molecule that forms the basic unit
for polymers. Eg. Amino Acids in Proteins; Nucleic
Acids in DNA/RNA
 Monomers bind to other monomers to form
repeating chain molecules through a process known
as polymerization

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Polymer Terminologies
 Monomer

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Polymer Terminologies
 Polymer
 A polymer is a substance or material consisting of
very large molecules, or macromolecules, composed
of many repeating subunits.
 Due to their broad spectrum of properties, both
synthetic and natural polymers play essential and
ubiquitous roles in everyday life.

Polyacetylene Polyethylene Terephthalate

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Polymer Terminologies
 Polymerization
 Polymerization is a process through
which a large number of monomer
molecules react together to form
a polymer.
 The macromolecules produced from
a polymerization may have a linear
or a branched structure.
 They can also assume the shape of a
complex, three-dimensional
network.

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Polymer Terminologies
 Functionality of Monomer
 In chemistry, functionality is the presence of functional groups
in a molecule.
 According to IUPAC, the functionality of a monomer is defined
as the number of bonds that a monomer's repeating unit
forms in a polymer with other monomers.
 Monomers with a functionality f ≥ 3 lead to a branching point,
which can lead to cross-linked polymers (a thermosetting
polymer).

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Polymer Terminologies
 Classification based on composition
 Homopolymers
 A homopolymer is a polymer where
every monomer unit (mer) of the chain is the same.
 Polyvinylchloride (PVC) is a homopolymer consisting
of vinyl chloride units.
 Polypropylene consists of repeating propylene units.

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Polymer Terminologies
 Classification based on composition
 Copolymers
 A copolymer is a polymer derived from more than
one species of monomer.
 The polymerization of monomers into copolymers is
called copolymerization. 
 Copolymers obtained by copolymerization of two
monomer species are sometimes called bipolymers.

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Polymer Terminologies
 Classification based on composition
 Copolymers
 Random Copolymer
 Alternate copolymer
 Block copolymer
 Graft copolymer

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Polymer Terminologies
 Tacticity
 Tacticity is the relative stereochemistry of
adjacent chiral centers within a macromolecule.
 The practical significance of tacticity rests on the
effects on the physical properties of the polymer.
 Based on arrangement of their substituent groups
polymers are classified as ,
 Random (Atactic) polymer
 Alternating (Syndiotactic) polymer
 Isotactic polymer

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Polymer Terminologies
 Tacticity Isotactic
 affects physical Same side
properties of the Eg. Polypropylene
polymer.

Relative
stereochemistry
of adjacent chiral
centers

Atactic
Syndiotactic Random arrangement
Alternating arrangement Eg. PVC, Polypropylene,
Eg. Natural Rubber polyethylene

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Classification of Polymers
 Based on origin
 Based on thermal behaviour
 Based on constituents
 Based on end use
 Based on performance-commodity, speciality,
engineering
 Based on composition
 Based on Tacticity

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Classification of Polymers
 Based on Origin
 Natural Polymer
 Natural Polymers are those substances which are
obtained naturally.
 Polymers are extensively found in nature. Our
body too is made up of many natural
polymers like nucleic acids, proteins, etc.
 Eg. Cotton, Silk, wood, rubber, etc.

 Synthetic Polymer
 Synthetic polymers are human-made polymers.
 They are commonly found in a variety of
consumer products. Various main chains and
side chains are used to make
different synthetic organic polymers.
 Eg. Polyethylene, PVC, nylon, etc
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Classification of Polymers
 Based on Thermal Behaviour
 Thermoplastic Polymer Thermoplastics

 A thermoplastic, or thermosoftening No links

plastic, is a polymer material that between
polymer
becomes soften on heating and stiffen chains
on cooling.
 Most thermoplastics have a high
molecular weight.
 Eg. Polystyrene, polyethylene,
polypropylene, etc.

Polystyrene foam PVC Pipes

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Classification of Polymers
 Based on Thermal Behaviour
 Thermoset Polymer
Links between
 A thermosetting polymer, often polymer chains
called a thermoset, is a polymer stops
which have resistance to heat movement
between them
softening, creep and solvent
attack.
 Curing is induced by heat or
suitable radiation and may be
promoted by high pressure, or
mixing with a catalyst.
 Eg. Epoxy resin, phenol
formaldehyde resin, etc Bakelite Jwellery Tools made of
Thermoplastics

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Classification of Polymers
 Based on Constituents
 Organic polymer
 The back bone chain of organic
polymer is essentially made up of
carbon atoms.
 Heteroatoms such as O, N, S usually
satisfy the side vacancies of carbon
atoms.
 Eg. Polythylene, polymethacrylate, Polydimethylsiloxane (PDMS)
etc.
 Inorganic polymer
 Back bone of inorganic polymers do
not contain carbon atoms.
 Eg. Polysiloxanes, polyphosphates,
etc. Polyphosphate

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Classification of Polymers
 Based on End use
 Fibres (eg. Nylon, polyester, etc.)
 Plastic (eg. Thermoplastics and thermosets)
 Elastomer (eg. Rubber, Buna-S, Buna-N, etc.)
 Films (eg. PP, LDPE, PVC, PET, etc.)
 Adhesive (eg. PVA, epoxy resin)
 Paints (eg. epoxy)
 Membranes (eg. Polyacetylene, polyaniline, etc.)

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 Applications of Polymers
 Plastics Applications in Automobiles
Interior Trim
Glass Interlayer (PP, ABS, PVC, PET) Panoramic Roof
(PVB) (PC)
Upholstery
Dashboard (PP, PVC, PUR)
(PP, ABS, PC)
Body
(reinforced epoxy,
PPO/PPE Alloys)
Lighting
(PC, PMMA, ABS, Wheel House
PBT) Radiator Support
(Phthalic Acid
resins)
Instrumental Bumper
Panel (PP, ABS, Under the Hood Fuel System Seating Door Handles
(PC/ABS,ABS) PC/PBT) (PA,PP, PBT) (HDPE, PA, PBT,(PUR, PP, ABS, PA) (PA, ABS, PC/ABS)
POM)

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Long forms of Polymers
 PVC – poly vinyl chloride
 PP – Poly propylene
 PC – poly carbonate
 ABS –Acrylonitrite butadiene styrene
 PBT – Polybutylene terepthalate
 PVB – polyvinyl butyral
 PET – polyethylene terepthalate
 PUR – Polyurethane
 POM – Polyoxymethylene
 PPO- poly (p-phenylene ) oxide
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Applications of Polymers
 Fibres

Nylon Rope
Water resistant
Polybenzimidazole (PBI) Modacrylic fibre
Polyester Fibre Fire fighter suit

Nylon Kevlar fibre

Spandex
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Applications of Polymers
 Furniture

Polycarbonate chair
PVC stools
PVC Kitchen Furniture

Polypropylene furniture
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Applications of Polymers
 Mattress

PU based memory foam

Polyurethane based Mattress

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Applications of Polymers
 Crockery

PET Bottles and jars Melamine formaldehyde

(melamine) crockery
Polystyrene Crockery

Polypropylene HDPE containers

Polypropylene Crockery Microwave containers
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Applications of Polymers
 Electronic Appliances

Silicones, PU, PC, PVC,

Polyesters used in making Acrylonitrile Butadiene styrene (ABS), PC, PP etc.
headphones

ABS (casing), glass reinforced Alkyd Resins, PF, UF etc. Ethylene vinyl acetate,
epoxy resin (Motherboard) polyphenylene oxide,
poly amides etc.

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Applications of Polymers
Biomedical Applications
Silicone Rubber, PU
rubber, Dacron
Polyester, Teflon, PC, PMMA, other acrylics
PMMA, pliable
hydrophilic plastics PVC, PMMA etc
(hydrogels)

Eye Implants Artificial teeth

Poly(α-cyanoacrylate)
based polymers Heart pumps Hip Joints
.
Silicone rubber, PE,
nylon, PET etc.
Tissue adhesives Artificial ligaments

Poly amino acids

Artificial Skin
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Applications of Polymers
 Biomedical Applications

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Applications of Polymers
 Water Purification

Ion-exchange resins are
insoluble polymers containing a
backbone of cross-linked
polystyrene and side chains of ion-
active groups
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Applications of Polymers
 Coating

Acrylic emulsion cement

Polytetrafluoroethylene (PTFE/Teflon)
coating for Automobiles
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Applications of Polymers
 Insulating material

Polypropylene thermal Polyethylene insulation for PVC insulated power cables

insulation sheets and pipes
panels

Acrylate polymers and Polyimide coated wire PVC insulation tape

polyimides used to coat
optical fibres
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Applications of Polymers
 Other Materials

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Properties of Polymers
 Mechanical Properties
 It is of great importance to be familiar with some basic
mechanical properties of the material before its application
in any field, such as:
 how much it can be stretched?
 how much it can be bent?
 how hard or soft it is?
 how it behaves on the application of repeated load etc.
 Mechanical properties of polymer depend on the following
factor:
 Strength
 Plastic deformation
 Abrasion resistance
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Properties of Polymers
 Mechanical Properties
 Strength
 In simple words, the strength is the stress required to break
the sample.
 Individual polymer chains are held together by weak
intermolecular forces of attraction.
 Low molecular wt polymers are soft and gum like, while
high mol wt polymers are tougher and more resistant to
heat.
 The polymers follow the following order of increasing
strength:
linear
linear < branched
< branched < cross-linked
< cross-linked < network < network

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Properties of Polymers
 Mechanical Properties
 Strength
 Strength of polymer also depends on presence of polar group like
OH, COOH, Cl, F, etc along the chain length.
 Intermolecular forces increases greatly due to presence of polar
group.
 Strength of polymer also depends on slipping power of molecule
over other.
 More the slipping power less is the strength of polymer.
 Hence PVC is tougher and stronger polymer than PE

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Properties of Polymers
 Mechanical Properties
 Plastic Deformation Strong
NOT tough
Strong &
 If a plastic material is loaded tough
beyond its elastic limit, it does not Stress

return to its original shape and size, Not strong

Not tough
ie., a permanent deformation
occurs.
 If the temperature is increased, a Strain
polymeric material changes from
brittle (crazing) to ductile (yielding)
behavior in deformation and
fracture.

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Properties of Polymers
 Mechanical Properties
 Abrasion Resistance
 Abrasion resistance refers to the ability of an
adhesive to resist wearing due to contact with
another surface.
 Wearing occurs when a hard rough surface slides
across a softer surface, usually the adhesive
material, causing the undesired removal of
material from the surface.

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Properties of Polymers
 Physical Properties

Physical State
of Polymer

Crystalline
Semicrystalline Amorphous
Ordered

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Properties of Polymers
 Thermal Properties- Glass transition temp
Glassy State

Hard Rigid
Solid
Stiffness/Modulus

Glass
Transition
Tg
(Mpa)

Rubbery
Iso viscous Flow
Viscoelastic
Soft
flexible
Viscous Rubbery State Viscous
Rubbery Flow
Extendable
Leathery Liquid
solid
Temperature (K)

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Properties of Polymers
 Thermal Properties
 In amorphous polymers there is no sharp melting point as of crystalline
polymers
 Crystalline polymers have large value for Tg as intermolecular forces
which held the polymer chains are very strong compared to amorphous
polymers
High Crystalline
Stiffness Amorphous
Modulus

Tg Moderate
Tg Stiffness

No Useful
Tm
Stiffness

Temperature
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Properties of Polymers
 Thermal Properties
 Effect of Intermolecular Forces
 Presence of polar side groups leads to strong
intermolecular attractive interactions between chains
 This hinders molecular motion and increases Tg
 For example consider –[CH2–CHX]–

X Tg (K)
–CH3 253
–Cl 354
–OH 358

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Properties of Polymers
 Thermal Properties

Tm = 265 ̊C Tm = 135 ̊C

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Properties of Polymers
 Thermal Properties
Restricted
Cross Links: Tg is directly proportional to Chain Mobility
degree of cross links

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Properties of Polymers
 Thermal Properties
 Molecular Weight: Tg is directly proportional to M.W. of Polymer
Shorter chains have more free volume, Tg for shorter chains will be
lower than Tg for long chains
 Plasticizer: Tg is inversely proportional to plasticization
Weaken intermolecular force between polymer chains reduces Tg
 Flexibility: Tg is inversely proportional to flexibility

Tg = −70 °C Tg = 69 °C
Presence of phenyl group increases rigidity

Presence of stiffening groups (such as amide, sulfone, carbonyl, p-phenylene etc.) in

polymer chain reduces flexibility

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Properties of Polymers
 Polymer dissolution

Solid polymer just Swollen polymer Solvated polymer

added to solvent in solvent molecules
diffusing out of
the swollen mass
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Properties of Polymers
 Molecular Weight of Polymers

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Properties of Polymers
 Molecular weight of polymers
𝑀𝑤
𝐷𝑒𝑔𝑟𝑒𝑒 𝑜𝑓 𝑃𝑜𝑙𝑦𝑚𝑒𝑟𝑖𝑧𝑎𝑡𝑖𝑜𝑛 ( 𝐷𝑃 )=
𝑀𝑂

Mw = Average molecular weight of the Polymer

MO = molecular weight of the repeating unit or the monomer

Polydispersity Index (PDI)

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Additives for Polymers
Light
Heat Stability
Stability Anti-stactic

Process
Stability Flame
Plastics = Retardants
Polymers
+
Additives Recycling
Fungicide

Copper
Biocide Scratch Contact
Resistance

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Commercially Important Polymers
 Epoxy Resins
 Also known as polyepoxides, class of reactive prepolymers and
polymers which contain epoxide group
 Both monomer and the polymer(before cross-linking) contain
epoxide group.
 Can form cross-links either with themselves or with wide range
of co-reactants (hardeners/curatives) including polyfunctional
amines, acids. Acid anhydrides, phenols, alcohols, thiols etc.
 Reaction with hardeners/curatives forms thermosetting
polymer

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Commercially Important Polymers
 Epoxy Resins Preparation
 Epichlorohydrin is used in excess to ensure epoxide groups at chain
terminal
 Many other compounds instead of Bisphenol-A are also used eg.,
glycols, glycerols, resorcinols etc.

Bisphenol-A Epichloro hydrin

Alkaline catalyst
at 60°C

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Commercially Important Polymers
 Epoxy Resins Properties & Applications
Surface coatings, skid resistant
Tough and excellent
surfaces for highways, road
resistance to heat and wear
junctions and round about

Low water adsorption tendency, Electronic applications

dimensional stability, good heat and (mouldings containing inserts
electrical resistance and ecapsulations)

Polar hence excellent adhesive

Adhesives for glass, metals etc.
characteristics

• Carried out quickly

• More economic than welding, screwing, rivetting etc.
• Joined surfaces free from corrosion
• Joins heterogeneous materials

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Commercially Important Polymers
 Elastomers or Rubber
 Synthetic Rubber (Polyurethanes/isocyanate)
Preparation
 Characterized by presence of urethane linkages
 Prepared by Addition growth polymerization
 Di-iso cyanide + diol
 Perlon-U - 1,6-hexamethyl diisocyanate + 1,4-butane diol

1,6 – hexamethyl diisocyanate

+
Polyurethane (Perlon-U)
1,4 – butane diol

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Commercially Important Polymers
 Elastomers or Rubber
 Synthetic Rubber (Polyurethanes)
Properties
 Low M.P. than polyamides due to increased flexibility
because of additional Oxygen atom
 Good resistance to Gas, Oil, and aromatic
Hydrocarbons
 High abrasion resistance,
 excellent resistance to O2 and O3
 Not Susceptible to microbial attack
 Not affected by dilute acids but affected by conc. acids

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Commercially Important Polymers
 Elastomers or Rubber
 Synthetic Rubber (Polyurethanes) Properties

With water in rxn mixture

Coatings Elastomers Fibres Foams

 Resistant to  Excellent abrasion • Popular
impact, resistance as
abrasion,  Good elasticity spandex  Flexible and rigid can be
greases, oils and hardness prepared.
etc.  Resistance to oils,  Light and tough.
greases and  Good resistance to
solvents weathering, abrasion
heat and chemicals

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Conducting Polymers

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Conducting Polymers
 Organic polymers are in general are bad conductors of electricity due to
absence of free electrons.
 1977 Heeger, MacDiarmid and Shirakawa reported that oxidation of
polyacetylene by Iodine increased its conductivity 108 fold (103 S/cm
approaching one of the best conductors)
I3−

• 2000

Insulators Semiconductors Conductors

(Polymers) (Undoped conducting (Doped conducting
Polymers) Polymers)

10−8 102 Siemens/cm

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Conducting Polymers
Conducting Polymers

Intrinsically Conducting Polymers Extrinsically Conducting Polymer

Can conduct electricity on its own Filled with metal powder/filaments,
graphite powder to make it conducting

Polymers with Doped Conductive element Blended conducting

conjugated π conducting filled polymers polymers
electrons Polymers •Polymer filled with •Conducting
•Delocalized π •Doped with carbon black, metallic polymers blended
electrons either electron fibres, metal oxides with conventional
•In Electric field π donors or •Polymer acts as polymers
electrons get acceptors binder •Better
excited and •Affects tensile physical/chemical/m
transported strength echanical props.

p-type n-type
Lewis Acid Lewis Base
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Conducting Polymers
 Intrinsically conducting polymers
Structural requirements
 Presence of conjugation (alternating σ and π bonds)
 Presence of aromatic rings
 Polymer should have Linear chains
 Such polymers have high crystallinity and planarity in structure

Aromatic with Heteroatoms

Conjugated π

Polyacetylene
X= NH Polypyrole
Aromatic + Heteroatoms
X=S Polythiophene
Conjugated π + Aromatic

X=NH Polyaniline
Polyphenylene vinylene X=S Polyphenylene sulfide
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Conducting Polymers
 Intrinsically conducting polymers
 Doping
p-type or Oxidative n-type or Reductive
3/2 I2 Na
(CH)n (CH)n+ I3− (CH)n (CH)n− Na+
Polyacetylene Polyacetylene chain Polyacetylene Polyacetylene chain
with positive charge with negative charge
 I2 in CCl4, FeCl3, Br2, AsF5,  Li, Na, naphthylamine, etc.
HBF4, HClO4 etc.

Protonic doping

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 Conducting Polymers
Antistatic
material
Rechargeable
Electrolytes
batteries

Molecular
Wires
Applications

Electronics

Optical
Filters Sensors Photovoltaic
Cells

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The End

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