Polymers

An Introduction to Polymer Chemistry

• Polymer (Greek: poly=many; mer=part)
• Made up of large molecules (high molecular weight)
characterized by repeating units called monomers (low
molecular weight) held together by covalent and non-
covalent bonds
• eg. Alkenes, vinyl chloride, ethylene glycol, diamines
• Polymerization
Fundamental process in which low molecular
weight compounds combine to form giant
molecules/ macromolecules of high molecular
weight
Synthetic polymers: eg polyethylene, nylon
Natural polymers: eg nucleic acids and proteins
 Degree of Polymerization
• Number of repeating units in the chain 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
• Data: If MW of PE, M = 28000,
MW of repeat unit, Mo = 28,
Calculate DP ???
M = nMo
• Thus, n = M/Mo
= 28000/28
= 1000
Degree of Polymerization (n) = 1000
 Classification
On the basis of origin
– Natural
– Synthetic
On the basis of nature of monomer
• Homopolymers (comprise of monomers of the same type)
– Linear
– Branched
– Cross-linked
• Heteropolymers/ Co-polymers (Different repeating units)
– Linear; Branched; Graft (regular/irregular); Block (regular/irregular)
On the basis of chemical nature
• Organic (polymer backbone chain made up of C atoms)
• Inorganic (No carbon atoms in the backbone chain, eg., Silicone rubbers)
Tacticity: Orientation of side groups on the monomeric
units in polymer takes place in orderly/disorderly fashion w.r.t
main chain. The difference in configuration affects their
physical properties
Isotactic:
Functional groups are all on the same side of the main
chain, FG= Y
molecules pack best with other molecules of the same shape
Syndiotactic: Functional groups occupy alternating position
Nice arrangement to make crystal pack

Atactic: Functional groups arranged in random manner

No regular array to make a nice crystal

For example, atactic polypropylene is a gummy solid, while

isotactic version is highly crystalline & tough.
 Addition Polymerization
• Monomers with double or triple bonds tend to
polymerize without the liberation of small
molecules.
• It yields product that is an exact multiple of the
original monomer unit (homo polymers)
• Polyethene (PE)
 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.
• Propagation: Process continues with successive addition of
monomer units to the chains

• Termination: Through a combination of two chains

 Name(s) Formula Monomer Properties Uses
Polyethylene ethylene
–(CH2-CH2)n– soft, waxy solid film wrap, plastic bags
low density (LDPE) CH2=CH2
Polyethylene ethylene electrical insulation
–(CH2-CH2)n– rigid, translucent solid
high density (HDPE) CH2=CH2 bottles, toys

Polypropylene propylene atactic: soft, elastic solid similar to LDPE

–[CH2-CH(CH3)]n–
(PP) different grades CH2=CHCH3 isotactic: hard, strong solid carpet, upholstery

Poly(vinyl chloride) vinyl chloride

–(CH2-CHCl)n– strong rigid solid pipes, siding, flooring
(PVC) CH2=CHCl

Poly(vinylidene chloride) vinylidene chloride

–(CH2-CCl2)n– dense, high-melting solid seat covers, films
(Saran A) CH2=CCl2

Polystyrene styrene hard, rigid, clear solid toys, cabinets

–[CH2-CH(C6H5)]n–
(PS) CH2=CHC6H5 soluble in organic solvents packaging (foamed)

Polyacrylonitrile acrylonitrile high-melting solid rugs, blankets

–(CH2-CHCN)n–
(PAN, Orlon, Acrilan) CH2=CHCN soluble in organic solvents clothing

Polytetrafluoroethylene tetrafluoroethylene non-stick surfaces

–(CF2-CF2)n– resistant, smooth solid
(PTFE, Teflon) CF2=CF2 electrical insulation

Poly(methyl methacrylate) methyl methacrylate lighting covers, signs

–[CH2-C(CH3)CO2CH3]n– hard, transparent solid
(PMMA, Lucite, Plexiglas) CH2=C(CH3)CO2CH3 skylights

Poly(vinyl acetate) vinyl acetate

–(CH2-CHOCOCH3)n– soft, sticky solid latex paints, adhesives
(PVAc) CH2=CHOCOCH3
cis-Polyisoprene isoprene requires vulcanization
–[CH2-CH=C(CH3)-CH2]n– soft, sticky solid
natural rubber CH2=CH-C(CH3)=CH2 for practical use

Polychloroprene (cis + trans) chloroprene synthetic rubber

–[CH2-CH=CCl-CH2]n– tough, rubbery solid
(Neoprene) CH2=CH-CCl=CH2 oil resistant
 Condensation/Step Polymerization

• Formation of polymers from polyfunctional monomers

of organic molecules with elimination of small molecules
like water, HCl, ammonia
• Functional group of one monomer unit reacts with
functional group of the other
• Some monomers have more than two reactive sites,
allowing for branching between chains, as well as
increasing the molecular mass of the polymer
Eg- Nylon-6,6 (hexamethylene diamine + adipic acid)

• Eg PET (polyethylene terephthalate)

• The linkage is a polyester linkage

• Note: the acid and the alcohol groups are still available for bonding
 Formula Type Components Tg ºC Tm ºC
~[CO(CH2)4CO- polyester HO2C-(CH2)4-CO2H <0 50
OCH2CH2O]n~ HO-CH2CH2-OH

polyester para HO2C-C6H4-CO2H 70 265

Dacron HO-CH2CH2-OH
Mylar

meta HO2C-C6H4-CO2H 50 240

polyester HO-CH2CH2-OH

Poly- (HO-C6H4-)2C(CH3)2 150 267

carbonate (Bisphenol A)
Lexan X2C=O
(X = OCH3 or Cl)
 Copolymerization
• Macromolecules composed of more than one monomeric repeating unit
• In this respect, it is useful to distinguish several ways in which different
monomeric units might be incorporated in a polymeric molecule.
The following examples refer to a two component system, in which one monomer is
designated A and the other B.
Statistical Copolymers Also called random copolymers. Here the monomeric units are distributed
randomly, and sometimes unevenly, in the polymer
chain: ~ABBAAABAABBBABAABA~.
Alternating Copolymers Here the monomeric units are distributed in a regular alternating fashion, with
nearly equimolar amounts of each in the chain: ~ABABABABABABABAB~.

Block Copolymers Instead of a mixed distribution of monomeric units, a long sequence or block of
one monomer is joined to a block of the second monomer: ~AAAAA-
BBBBBBB~AAAAAAA~BBB~.
Graft Copolymers As the name suggests, side chains of a given monomer are attached to the
main chain of the second
monomer: ~AAAAAAA(BBBBBBB~)AAAAAAA(BBBB~)AAA~
 Addition Copolymerization
• Radical or addition polymerization gives a statistical
copolymer.
• Eg. Styrene-Butadiene rubber (Buna-S)
 Plastics

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
• Egg yolk, polyester, resins, polyurethanes, UF resin
Thermoplastic polymers Thermosetting polymers
They soften on heating and harden They are fusible on initial heating,
on cooling but 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 Insoluble in organic solvents
solvents

Moulded articles are taken out after Moulded articles are taken out from
cooling the mould to avoid the mould even when they are hot.
deformation of the article
Melting and Glass transition temperatures
Melting is a transition which occurs in crystalline polymers. Melting happens when the
polymer chains fall out of their crystal structures, and become a disordered liquid.

The glass transition is a transition which happens to amorphous polymers, polymers

whose chains are not arranged in ordered crystals, even though they are in the solid
state.
The crystalline polymers will have some amorphous portion within it. This portion
usually makes up 40-70% of the polymer sample. Hence the sample of a crystalline
polymer can have both a glass transition temperature and a melting temperature. The
amorphous portion undergoes the glass transition , and the crystalline portion
undergoes melting .
 Melting and Glass transition temperatures
The glass transition temperature Tg is the temperature
above which there is a reversible transition
in amorphous materials (or in amorphous regions
within semi crystalline materials) into a molten, viscous
or rubber-like state (viscoelastic state)
When the polymer is cooled below this temperature Tg, it
becomes hard and brittle, like glass.
• Temperature below which polymer becomes soft, flexible and
viscoelastic is (Tg)
• Temperature above which polymer becomes liquid or viscofluid in
state is (Tm)
 Melting and Glass transition temperatures

Hard plastics like polystyrene and polymethyl methacrylate are

used well below their glass transition temperatures, that is in
their glassy state.
Their Tg values are well above room temperature, both at
around 100 °C (212 °F).

Rubber elastomers like polyisoprene and polyisobutylene are

used above their Tg, that is, in the rubbery state, where they are
soft and flexible.
Their Tg values are well below room temperature
 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.
 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)
• 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 H2O2, benzoyl peroxide, ZnO, NH3, 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
 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
PMMA (Polymethyl methyacrylate)

Acetyl peroxide/ hydrogen peroxide

(Ester of methyl acrylic acid)

 Properties and Uses
• Hard rigid material with high softening point
• High resistance to sunlight
• High optical transparency
• Low chemical resistance to hot acids and alkali
• Low scratch resistance

• Making lenses, jewelry, artificial eyes, dentures

• Aircraft light fixtures, automotive appliances
• Paints, adhesives, emulsions, T.V screens, guards
 Elastomers
• Amorphous polymer with high degree of elasticity 
deformed by stretching & regain original form when
stretching force is removed
Natural Rubber (cis-Polyisoprene)

amorphous solid, translucent, impervious to gases, elastic in nature

low tensile strength, elasticity over a narrow range of temperature
• 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
 Applications of rubber

a) Due to remarkable resistance to electricity, it is used as

an insulating coating on wires and cables, used for electric
power transmission.
b) Due to its elasticity, it is used to fabricate rubber bands,
rubber goods, golf balls, tubes for automobiles, etc
c) It acts as an excellent adhesive
d) Foam-rubber is used for making pillows, cushions,
mattresses, automotive pads, etc.
e) Polysulfide rubber is used as a solid-propellant fuel for
rocket motors
 Drawbacks of Natural Rubber

• It softens at high temperature and becomes brittle at

low temperature (plastic in nature)
• Less tensile strength
• It is attacked by acids, oxidizing agents, non-polar
solvents and oxidized by air.
• Large water absorption capacity
• It swells in organic solvents and gradually disintegrates
• It possesses marked tackiness
Vulcanization
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
Water absorption large small
Useful temp. range 10 to 60 C - 40 to +100 C
Tackiness marked slight
Swelling in organic Infinite (soluble) Large, but limited
solvent
Quality Inherent Can be controlled by vulcanization
Preparation, Properties and Uses of
Commercial Rubbers
 Buna-S Rubber/ GR-S/Cold Rubber

75 parts 25 parts

• Copolymerization of butadiene & styrene carried out at 5oC

• Can be vulcanized with less sulphur
• Good and tough mechanical properties (high abrasion resistance,
high load bearing capacity)
• Easily attacked by oxidizing agents, mainly ozone, organic solvents

Uses: Manufacture of tyres, insulating wires and cables, adhesives

 Polyurethane rubber/ Isocyanate rubber

• Ethylene glycol polymerizes with ethylene diisocyanate to form

polyurethane rubber.
• Highly resistant to oxidation
• Foams are resistant to heat, abrasion, chemicals and weathering
• Resistant to organic solvents, attacked by acids and alkali
Uses: surface coatings and manufacture of foams and fibers
 Conducting Polymers
• Polymers are poor conductors of electricity, due to
non-availability of large number of free electrons
• Polymers with polyconjugated structures are insulators
in pure state, but can be converted into polymers with
electrical conductivities comparable to metals.

Polymers today are synthesized at par to conductivities

of metallic conductors
Conducting polymers are finding increased use due to
their light weight, easy to process and good mechanical
properties.
 Conditions
• Excitation of  electrons in electric field
- Polymer should consist of alternating single and
double bonds called conjugated double bonds
• Disturbance in polymer matrix by
- Either by removing electrons from material
– Or inserting electrons into the material.
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
 Types of conducting polymers
1. Intrinsically conducting polymer (ICP)

• Polymers with conjugated  electrons

• In an electric field the electrons get excited and are

transported through solid polymeric matrix.

• Overlapping orbitals of conjugated  electrons over the

entire polymer forms valence and conduction bands
2. Doped conducting polymer
Polymer matrix has to be disturbed –
• Removing electrons (oxidation) by electron acceptors like
AsF5, Iodine, etc
• Inserting electrons(reduction) by electron donors like alkali-
metal ion Li, Na, Ca

• The conductivity is increased by creating either a positive or negative charge on the

(i) P-doping: treating ICP with Lewis acid, thereby oxidation process
sets in and positive charge created on polymer backbone.

• Iodine molecule attracts an electron from polyacetylene chain and

becomes I3-
• Polyacetylene molecule, now positively charged is a radical cation
• 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–
(ii) N-doping: treating an ICP with a lewis base, thereby reduction
process takes place and negative charge created on polymer
backbone

Examples:
• Industrially conducting polymers are: Polyquinoline,
polyanthrylene, polythiophene, polybutadienylene, polyacetylenes
etc
• Used in making button cells, photovoltaic devices, sensors,
biomedical devices.
 3. Extrinsically conducting polymers
(i) 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
(ii) Blended conducting polymer: This polymer is made by
blending a conventional polymer with a conducting polymer
4. Coordination conducting polymers
A metal atom with polydentate ligand, which is a charge transfer
complex is bound to the polymer to make it conducting.
 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.
Whether used as fuels or a source of recycled plastic, plastic waste must be separated
into different categories.
To this end, an identification coding system was developed by the Society of the
Plastics Industry (SPI) in 1988, and is used internationally. This code, shown on the
right, is a set of symbols placed on plastics to identify the polymer type, for the purpose
of allowing efficient separation of different polymer types for recycling.

PETE HDPE V LDPE

polyethylene high density polyvinyl low density

terephthalate polyethylene chloride polyethylene

PP PS OTHER

polyesters, acrylics
polypropylene polystyrene
polyamides, teflon etc.