Polymers

What we will learn?

 Polymers & their advantage over
traditional material
 Classification of polymers
 Properties of polymers & their structure-
property relationship
 Molecular shape and crystallinity
 Glass transition temperature
 Thermoplastic and thermosetting
polymers
 Different fabrication techniques
 Elastomers & its structure
 Synthesis of common polymers
 Conducting and semiconducting polymer
Monomer: They are simple molecules, which combine with each other to form polymer.
 Ethylene, Methyl methacrylate, Vinyl chloride

Polymer: It is a macromolecule formed by the repeated unit of several simple molecules.

 Polyethylene (PE), Polymethyl methacrylate (PMMA), Polyvinyl chloride (PVC)

Polymerization: It is the process of conversion of substance having low molecular weight into substances having high
molecular weight with or without the elimination of byproducts.
Degree of polymerization (DP): The number of repeating units present in a polymer is called degree of
polymerization.

 “n” could be in the range of hundreds and thousands – then the polymers are high polymers.
 n<10, they are oligomers.

Functionality: The total number of reactive sites or functional groups present in a monomer molecule is called the functionality
of monomer.
o Ethylene, Adipic acid – bifunctional
o Glycerol, Phenol - trifunctional

Natural polymers: Polymers obtained from natural sources.

 Wool, cotton, silk, proteins, natural rubber, polysacchrides

Synthetic polymers: Polymers synthesized from simple molecules.

 PE, PMMA, PVC, Polytetrafluoroethylene (PTFE), Polycarbonate (PC).

Thermoplastic polymers: Polymers that soften on heating and which can be converted into any shape on cooling are called
thermoplastic polymers.

 The process of heating, reshaping and retaining on cooling can be done several times
 PE, PMMA, PTFE, PC etc.
Thermosetting polymers: Polymers that undergoes chemical changes and cross-linking on heating and
become permanently hard, rigid, infusible on cooling, are called Thermosetting polymers.
 Phenol-formaldehyde (Bakelite), Urea-formaldehyde, epoxy resin etc.
Addition polymers: Polymers that forms by self-addition of several monomers to each
other without elimination of byproducts are called addition polymers.
 PE, PVC, PMMA etc.
Condensation polymers: Polymers that forms by intermolecular condensation reaction by
the functional groups of the monomers with continuous elimination of small molecules,
such as water, ammonia, methanol are known as condensation polymers.
 Polyesters, Epoxy resin, Nylon-6,6; etc.

Linear polymers: They are the polymers that obtained from bifunctional monomers and
“epoxy” glue
after polymerization yielded linear structure.
 HDPE, All thermoplastics
Branched polymers: When bifunctional monomer is polymerized with a little amount of trifunctional monomer, then branched
polymer is formed. It contains a linear backbone with branches arising randomly from it.
 Low-density Polyethylene, Polystyrene etc.
Cross-linked polymers: When functionality of monomer is three and above, a three-dimensional polymer
network is formed which is known as cross-linked polymers.

 Bakelite, Urea-formaldehyde etc.

Organic polymers: A polymer whose backbone chain is made of carbon atoms are termed as organic polymers. The atoms
attached to the side valencies of the backbone carbon atoms are H, O, N etc.

 Majority of synthetic polymers – PE, PVC, PMME etc.

Inorganic polymers: A polymer that don’t contain carbon atom in their backbone chain is termed as inorganic polymers.

 Silicone [-(Si(Me2)O)n-], Polyboron nitride [-(B=N)n-], Polythiazyl [-(S=N)n-]

Atactic polymer: On the basis of the configuration, when a polymer

contains its side chain randomly around its main chain are termed as
atactic polymer.
Isotactic polymer: When a polymer contains its side chain at the same
side of its main chain are termed as isotactic polymer.
 Syndiotactic polymer: When a polymer contains its side chain in alternating fashion of its main chain
are termed as syndiotactic polymer.

Elastomers: The polymers which undergo very long elongation when pulled apart
and returned their original length on release are called elastomers.

 Mainly coiled & long-chained polymer with van der walls force.
 Natural rubber, Buna-S, Butyl rubber etc.

Fibers: The polymers which are long, thin, thread-like polymers whose length is at
least 100 times their diameter, are termed as fibers.

 Don’t undergo stretching and deformation and linked with H-bonding.

 Natural jute, wood, silk and synthetic polymer – nylon 6,6 and terylene

Resin: The low molecular weight polymers generally used as adhesives.

 Epoxy resin, Urea-formaldehyde etc.

 Liquid or powder form
Plastics: Polymers which can be molded into desired shapes by the application of heat and pressure.
 PE, PVC, PC, Teflon etc.
 Homopolymers: The polymers which formed from the same type of monomers are called
homopolymers.
 PE, PMMA etc.

Copolymers: When two or more different types of monomer make up the polymer, it is known as copolymer.
 Styrene-Butadine (SBR), Styrene-Acrylonitrile (SAN), Acrylonitrile-
butadine-styrene (ABS) etc

Types of Polymerization
Addition (chain Growth) Polymerization:
A polymerization reaction in which monomers containing one or more double bonds are
linked to each other without elimination of any byproduct, usually in presence of free
radical initiator, is called addition polymerization.

 Olefinic or vinyl compounds undergo addition polymerization

 Rapid addition takes place by an initiator
 No by product elimination.
Condensation (Step Growth) Polymerization:
A polymerization reaction in which bifunctional or polyfunctional monomers undergo
intermolecular condensation with continuous elimination of byproducts, is called condensation
polymers.

 Polymerization is catalysed by acids/alkalis

 Continuous elimination of by-product such as water, ammonia
 Polymerization is slow & stepwise
 Elemental composition is different for both reactants and product
 Copolymerization: The polymerization of two or more different monomers resulting in the
formation of a polymer containing both the monomers linked in one chain is called
copolymerization.

 Considered as a type of addition polymerization

 Differs from the "simple" polymerization reaction in that, instead of a monomer, a mixture of two or more chemically
different monomers is used

Some Useful Copolymers

Monomer A Monomer B Copolymer Uses
H2C=CHCl H2C=CCl2 Polyvinylidene chloride (PVDC) films & fibers
Types:
 Block copolymer: H2C=CHC6H5 H2C=CH-CH=CH2 SBR (styrene butadiene rubber) tires
 Random copolymer: H2C=CHCN H2C=CH-CH=CH2 Nitrile Rubber Adhesives hoses
 Graft copolymer:
H2C=C(CH3)2 H2C=CH-CH=CH2 Butyl Rubber inner tubes

F2C=CF(CF3) H2C=CHF Viton (fluoroelastomer) gaskets

 Structure-Property Relationship of Polymers
 Structure depends upon
 Size of polymer chain
 Shape of polymer chain
 Chemical nature of the monomer

 Effect of Structure
 Physical & Chemical property

 Strength
Melt viscosity, impact & tensile strength – mechanical properties of polymer
 Tensile strength & impact strength α molecular mass

 Polymer is commercially useful if have high tensile strength and low

flow/melt viscosity
 Crystallinity
 Polymer have crystalline and amorphous parts
 Degree of crystallinity of the polymer depends upon its structure
 linear polymer have high crystallinity. (HDPE is more crystalline than LDPE which is more as
compared to polystyrene).
 Polymer chain having polar group have high crystallinity.
 Isotactic & Syndiotactic polystyrene is highly crystalline.

Elasticity
 Uncoiling & recoiling on application of force
 Breaking can be avoided by: cross linking, avoiding bulky groups, introducing non polar group
 Polymer chain having polar group have high crystallinity.
 Non-Elastic Nature
 Due to crystallizablity
 Chain mobility is reduced due to cross linking
 Polar group & aromatic/cyclic group impart strength (Nylon 6,6)

Plastic deformation
 Studied with application of temp. & pressure
 Thermoplastic deformation (Plastic deformation), due to linear structure, weak force
 Thermosetting polymer : no deformation

Chemical resistivity
 Depends upon structure of polymer and nature of attacking reagent
 Depends upon presence of polar/non-polar group, molar mass, degree of crystallinity
 Higher molecular mass less is dissolution
 Increase crystallinity increases chemical resistivity
 Glass Transition Temperature (Tg)
 Temperature below which a polymer is hard, brittle (glassy) and
above which it is soft, flexible (rubbery)
 Glassy State: No segmental or molecular movement
 Rubbery State: segmental motion but no molecular movement

Factor Effecting Tg:

Flexibility: Linear chain (C-C, C-O, C-N) provide freedom to rotation. Large group hinder the rotation & thus increase Tg.
Side Group: (eg: poly α-methyl styrene/polystyrene)extra methyl group restrict rotation
Intermolecular forces: Polar group Inc. intermolecular forces, restrict segmental/molecular mobility, increase Tg.
Branching & cross linking: Small branching reduce Tg & vice-versa
Plasticizer: Reduce the Tg value
Stereo-regularity: Tg increasing with increasing in Stereo-regularity
Molecular weight: Tg increases with increasing in molecular weight
 Significance of Tg:
 Flexibility measure
 Idea of thermal expansion, heat capacity, RI, electrical & mechanical properties
 Tells about the nature of polymer
 Tg & Tm Provides the knowledge about fabrication of material
 Plastics:
Polymers with high molecular mass, produced by natural or synthetic organic compounds.

Derived from Greek word “plastikos” mean capable of being mould or shaped
 Classification of Plastics:
Thermoplastic Thermosetting

Formed by addition Formed by condensation

Linear chain with negligible cross-link
Reversible change on heating
Soften on heating
Soft, weak & less brittle
Soluble in org. solvents
Low molecular weight
Reshaped & reused
No change in chemical composition
3D network, covalent bonding
Irreversible change on heating, degrade
Doesn’t soften on heating
Hard, strong & more brittle
Insoluble in org. solvent
High molecular weight
Can’t be reshaped & reused
Change in composition while molding

PE, PVC, PTFE Bakelite, Epoxy

 Plastic Molding Method:
Shaping the plastic to desirable shape & size
Material is heated, shaped & then cooled (Thermoplastic)
 Thermosetter are molded quickly

Thermoplastic molding:
Injection molding
Extrusion molding
Compression molding
Thermosetting molding:
Compression molding
Thermoplastic molding: Plastic Molding Method:
Injection molding
Extrusion molding
Compression molding
Thermosetting molding:
Compression molding

Advantages:
• High speed production
• Low production cost
• Minimal loss of material
• High precision
• Flexibility to make parts with complex shapes
Applications:
• manufacture bottle caps
• mugs
• dustbin
• chairs
• automotive dash boards
• etc
Thermoplastic molding: Extrusion molding
Injection molding
Extrusion molding
Compression molding
Thermosetting molding:
Compression molding

Applications:
• manufacture tubes
• rods
• plumbing pipes Advantages:

• electric cables • Low initial setup cost

• door insulation seals • Fast setup time

• optical fibers • Lowers production cost

 Compression Molding

Advantages:
• Low initial setup cost
• Minimum loss of material
• Good surface finish
• Fast setup time

Applications:
• Manufacture electric parts switches, switch boards, buttons
• Cooker handles
• Electronic device cases
• Appliance housing
• Large container
 Commercial Thermoplastics

Polyethylene (PE)
 Generally Homopolymer of ethylene or copolymer of ethylene
 Addition polymerization
 LDPE (40-60 % crystallinity) & HDPE (90 % crystallinity) are homopolymers

LDPE (Low Density PE)

 Linear polymer with branching
 High pressure (1K-3K atm) & temperature (80-350 0C) required
 Initiator such as benzyol peroxide or oxygen are used
 Process may be continuous or batch wise
 Properties
 White, waxy & translucent, with low density
 It melts in 107-120 0C. Tg is -120 0C
 Flexible & tough over wide range of temperature
 Chemically inert
 Resistive against acids/bases
 High impact strength, low brittleness, transparency and electrically insulated

Applications
 Transparent film
 Squeeze bottle
 Paper coating
 wrapping
 table clothes
 Container & sheets
 Cable wire & insulation
 HDPE (High Density PE)
 Linear polymer with little or no branching
 Low pressure required, low temp (< 100 0C)
 Ziegler-Natta catalyst (Al(C2H5)3 .TiCl4) used, coordination polymerization occurs (Philip process)

Applications
 Dustbin

Properties  Milk bottle

 High density  Cans

 Melt in temp. range of 130-138 0C, Tg is -20 0C  Drums

 Higher rigidity than LDPE  Containers

 Better chemical resistance  Fuel tanks

 More stiff, tough, tensile strength, hardness, heat resistant  Pipes

 Opaque, less impact strength, but better barrier properties  Cable insulation
 PP (Polypropylene)

 Linear polymer with little or no unsaturation

 Low pressure required
 Ziegler-Natta catalyst (Al(C2H5)3 TiCl4) used
 90 % or more of the polymer is isotactic form
 Monomer are added in head to tail fashion

Properties Applications
 High density
 Fiber
 Melt in temp. range of 165-170 0C  Automotive/appliance components
 Packaging containers
 Electric properties are same as PE
 furniture
 Low cost polymer  Toys
 Pressure sensitive tape
 Inert to water & microbes
 Revertible pouches
 Shrink films
 PS (Polystyrene)

 Bulk/Suspension polymerization of styrene

 Free radical polymerization

Properties Applications
 Rigid, transparent, thermoplastic  Household wares
 Amorphous polymer  Combs, toys
 Radio, TV parts
 Offers stiffness & dimension less stability  Video cassettes
 Moisture resistant  Refrigerator parts
 Electric insulation material
 Electrical insulator, good colorability & moldability  Thermocol
 PVC (Polyvinyl Chloride)
 Free radical polymerization
 80 % polymerization is suspension else is emulsion polymerization
 Needs 50-75 oC
 Most versatile due to its blending ability with plasticizers, stabilizers &
different additives

Properties
 Colorless, odorless, non-flammable, chemically inert
 Resistant to light, Oxygen, acids & alkali Applications
 Offers greater stiffness compared to PE
 Building & construction
 Pipes, flooring & vinyl siding
 Wire, cable insulation
 Packaging
 Flexible films, pool lining
 Artificial leather, wall covering
 Electrical outlet boxes, automotive bumpers
 PTFE (Polytetrafluoroethylene)/TEFLON
 Linear polymer
 Emulsion polymerization , peroxide initiator

Properties
 Highly crystalline
 High melting point, high temp. stability, low temp. flexibility Applications
 Low friction, remain slippery  Insulation of motor, generator, wires, cable

 Insoluble in any solvent  Coating in food processing units

 Electrical insulate  anti corrosive coat in weapons

 gasket, industrial filters, belts, non lubricated bearing
 Cardiovascular grafts, heart patches
 Ligament of knees
 Phenol Formaldehyde Resin (Bakelite)
 Condensation polymer
 Phenol & formaldehyde reaction using base/acid
 Product depends upon conc. of reactant & type of catalyst used

Alkaline catalyst Resol

Acid catalyst
Novolac

Properties Applications
 Electric equipment parts
 Bakelite is rigid, hard, scratch resistant  cooker handle
Telephone parts
 Electrically insulative
Golf ball
 Thermal stability up to 200 0C Head of typewriter
Adhesive for plywood
 Resistant to water, low flammability
Lamination of cardboards & wood
Phenol Formaldehyde Resin (Bakalite)
 Elastomers (Rubbers)
 Polymer which can undergo long elongation & get back to original shape (elasticity)

Natural Rubber

 Prepared from latex

 Linear polymer of isoprene

Drawback of NR
 Hard and brittle at low temp. and
soft & sticky at high temp.
 Poor storage capacity
 High water absorption capacity
 Weak tensile strength
 Suffers permanent deformation
 Sensitive towards oxidation
 Elastomers (Rubbers)
 Rubber becomes more durable with better mechanical properties
 Sulphur crosslinking occurs between the polymer chain
 It brings stiffness & prevent intermolecular sliding Properties
 Good tensile strength, electrically insulator
 Synthetic Rubber  low water absorption capacity
Buna-S (Styrene-Butadiene rubber)  Higher resistance towards oxidation, wear & tear
Buna-N (butadiene-acrylonitrile)  Resistive towards solvent (Org.) petrol, benzene, oil, CCl4
Synthetic and Semi-synthetic Fibers
 Nylons - Polyamide
Properties
 Contain H-bonding, makes it crystalline
 Chemically stable, resistant to abrasion
 can be spun into fiber, which is tough,
moisture resistant

Applications
 Making sports gear, fishing lines, sports equipments
 Making brushes and comb
 Provide insulation to equipment
 Bearings
 Cords of tyres
 Fabric for clothes
 Conducting Polymers

Trans-Polyacetylene
Poly(para-phenylene)
Poly(para-phenylene vinzlene)

Polythiophene

Polypyrrole
 Polyacetylene

Oxidizing agent/I2
+I2

4.4*10-5 S/cm 400 S/cm

I2

Polaron

e- + I 2 + ½ I I3 -

Polyaniline

Soliton
 Composites
 Assembly of two or more components in order to obtain specific characteristic properties is
termed as composite materials.
 The components do not dissolve or merge completely into each other; instead they act
together while retaining their individual identities.

 Matrix Properties of Composite used

 Fillers/Reinforcing agents in aircraft applictaion
Low density
 High strength & stiffness
 good abrasion
 Impact resistance
Classification  Corrosion resistance

Matrix constituent Reinforced form

 OMCs (Organic matrix composites)
{Polymer matrix (PMC) and carbon matrix (CMC)}
 MMCs (Metal matrix composites)
 CMCs (ceramic matrix composites)
 Fiber reinforced composites
Continuous & Discontinuous (prop. vary with length)
 Laminar composite (sandwiched structure)
 Particulate composite (Particles, like flakes or powder eg;
concrete, wood particle board)
 Fiber Reinforced Plastics (FRP)
 Composites of fiber & polymer matrix
 Fiber are source of strength, polymer matrix glue the fiber together
 Fillers & modifiers are added to smoothen the properties

 Common reinforce agents: Al, Al2O3, Aluminium silica, asbestos, graphite, glass etc.

 Polymer matrix: Acrylonitrile butadiene (Buna-N), Nylon, PE, PP, Polyethylene terephthalate (PET), Polyester,
polyurethane, epoxy etc.

Applications
 In cars n aircrafts, due to light weight
 Making bridges (graphite epoxy), due to strength
 Cars & boats, due to corrosion resistance
 Archery bows, due to flexibility
 Armors, due to high strength
 Building insulation, automobile compartment, due to
thermal resistance