CY-1001

POLYMERS
 Reference Books

• A Textbook of Polymer Chemistry by M S Bhatnagar (ISBN-

13: 978-8121932301)

• Principles of Polymerization by George Odian. (ISBN 0-

471-27400-3)
 Why Study Polymer Chemistry ?

Carry Bags Pipes

House hold Items Soft Drink bottles

Electrical Medical

Aerospace application
Increasingly replaced conventional material such as
wood, metals, stone, ceramics

Lighter along with excellent strength

Design Flexibility

Long-term stability

Thermal and electrical insulator

Optical clarity

Multifunctional and tunability

 Introduction to Polymer
 Polymer: substance build up by a large number of small
repeating units (monomers) joined together by chemical bond.

 Greek word; Polys→ Many & Meros → Part

Monomer: The molecule from which a polymer is synthesized

H H H H H H

Monomer C C C C C C

H H H Cl H CH3
 Terminology in Polymer Science
Monomer: The small molecules that combine each other to form polymer
molecules.

Repeating unit: It is a part of a polymer whose repetition would produce the

complete polymer chain by linking the repeat units together successively
along the chain, like the beads of a necklace.

Degree of polymerization: It represents the number of repeat units in a

polymer chain (DP = Mn /molecular weight of the repeat unit)

Homopolymers: The polymer which is made from a single monomer unit

Copolymers: Multiple monomers reacts together to form the copolymer

Molecular weight: express in terms of number-average M.W. (Mn) and

weight-average M.W. (Mw).

Polydispersity index: PDI = Mw/Mn; PDI ≥ 1 for synthetic polymers.

 Polymer Molecules

 Large, gigantic molecules also called macromolecules.

 With in each polymer molecules the atoms are bonded by
covalent inter atomic bonds.

(A perspective of Polyethylene molecule indicating Zigzag backbone structure)

C-C bond length is 0.154 nm and the bond angle is 109o

 Polymer molecules
Polymerization:
 Process by which simple monomer molecules joined
together to form polymer.
H H
H H
polymerization
n C C C- C
H H H H
n
Ethylene
Mol wt = 28 Polyethylene

n = degree of polymerization (DP) ≥ 104

DP = No. of repeating unit in the polymer chain

Average mol. wt = Mol wt of repeating unit x DP

For PE, Average Mol wt = 28 x 104
 Polymer Molecules

Constitutional Repeating Unit (CRU) = The smallest structural

repeating unit constituting the polymer is called CRU.
The CRU of a PVC is
H H H H
H H C C
C C
C C H Cl
H Cl
H Cl n Or
PVC CH2 CH
Monomer
Cl

CRU

Q1. Illustrate the monomer structure, Av mol wt and

CRU for the polymer Polystyrene, Given DP = 106 ?
Q.1 Answer

Polystyrene Styrene CRU

Monomer

Given, DP= 106

Av. Molecular Wt=104 X 106
 Functionality in polymer chemistry
 The functionality of a monomer is defined as the no. of bonds
that a monomer/repeating unit forms in a polymer with other
monomers.

 In case of functionality of f=2, a linear polymer is formed by

polymerisation.
 Example-

O O
H2 H2 H H2 H2
H2N C NH2 HOOC C COOH N C NH C C C

6 4 6 4 n
Hexamethylenediamine Adipic acid
 Monomer Functionality
Q. Can all types of molecules be used as monomer?
Ans: Not
A Substance can be acts as monomer only if It has
bifunctionality. i.e. It may have a double bond or two
reactive functional groups

Examples: (i) CH3 CH3 X

(II) n CH2 CH2 CH2 CH2

n
Functionality: The number of bonds a monomer can form
Bifunctional : ethylene (polyethylene)
Trifunctional: Three active bonds (phenol-formaldehyde, Bakelite)
 Monomer Functionality

Lets consider the chemical reactions between two molecules

each having single functionality. Are they form polymer ?

However, the reaction between two bifunctional molecules leads

to formation of high molecular wt polymer.

Example:
 All the above examples suggest that bifunctionality in a
monomer is must for the growth of a polymer chain.

 Again, Reaction between two bifunctional molecules form

Linear Polymer.

 Bi-functional & Tri-functional molecules form Branch or

Cross-linked polymer .
 Polymer Classifications
There are several ways to classify polymers. The classifications
are based on several considerations.

Source/Origin
Natural or Synthetic polymer
Polymer Classifications

Types of Polymerization Addition & Condensation

Polymerization
Conductance Conducting and Insulating
Polymers
Environmental
Friendly
Biodegradable & Durable

Types of Atoms Organic & Inorganic Polymer

Number of monomer
Homopolymer & Copolymer
 Structure/Shape Linear, Branched or Cross-linked
Polymer Classifications

Response to heat
Thermoplastics and Thermosets

End use
Fibers, Plastics and Elastomers

Physical state
Crystalline and Amorphous polymers

Stereochemistry Isotactic, Syndiotactic & Atactic

Polarity
Polar & non-polar Polymer
Source/Origin
Natural or Synthetic polymer

Natural Polymer
 Polymers that occur in nature are called Natural Polymer.
 Many naturally occurring polymers include wood, rubber,
cotton, starch, wool, Leather, Proteins and silk etc.
 They are also called as Biopolymers
Proteins: Polymer of Amino acids

Amino acid

O
C N

H
n
Polypeptides or proteins
Source/Origin
Natural or Synthetic polymer Biopolymers
Cellulose & Starch- Polymer of D-Glucose

Branched Structure

Structure of Starch
α – (1 → 4) Linkage

D- Glucose β –D Glucopyranose
α –D Glucopyranose
 Source/Origin
Natural or Synthetic polymer
Biopolymers
Structure of Cellulose

Cellulose is a linear chain of several hundred to over

ten thousand β(1→4) linked D-Glucose units

Like starch, cellulose is a polysaccharide with glucose as its monomer.

However, cellulose differs profoundly from starch in its properties
 Source/Origin
Natural or Synthetic polymer

Synthetic Polymers
 They are artificial or man made polymer.

Examples:
H H
CH-CH2
H H
C C
C C n
n
H H H Cl n

PE PVC PS

PTFE or Teflon Terylene

Source/Origin
Natural or Synthetic polymer Semi-synthetic polymers

Examples: Cellulose
Cellulose Acetate
& Cellulose nitrate

Cellulose nitrate

Cellulose acetate
21
Types of Polymerization
Addition & Condensation Polymerization

Addition Polymerization
(Chain reaction or chain growth)
 Unsaturated monomer usually follows addition polymerization.

 No reaction byproduct is obtained.

Examples:
H H CH-CH2
H H
C C C C
n
H Cl
n
n H
H

PVC Polyethylene
Polystyrene
Types of Polymerization
Addition & Condensation Polymerization

Condensation polymerization
(Step reaction or step growth)
 Monomers containing reactive functional group undergo
condensation polymerization.

 Elimination of small molecules (i.e. water, alcohol etc.) takes

place.
Example: Nylon 6,6; Terylene (PET).
O O O O

NH-(CH2)6-NH-C-(CH2)4-C C C O- (CH2)2-O

n n
Conductance
Conducting and Insulating Polymers

Insulating Polymers

 Most of polymers are poor conductor of electricity, because

of non- availability of free electrons in conducting process.

 Examples: Poly styrene, Nylon, PVC, PolyEthylene etc.

Conductance
Conducting and Insulating Polymers

Conducting polymers
 A polymer which can conduct electricity is term as
conducting polymer.

 They have conjugated π electrons in its backbone chain

that increases the conductivity.

 Example-
Polyacetylene (PA),Polyaniline(PANI), Polypyrrole (PPy),
Polythiophene (PTH), Poly(para-phenylene) (PPP),
Poly(phenylenevinylene) (PPV), and Polyfuran (PF).
Conductance
Conducting and Insulating Polymers

Conducting polymers
H-C C-H HC CH
n
Polyacetylene

CH CH CH CH
NH
N n
n Hoping (moving) of electron
H
Polyaniline
Polypyrrole
Types of Atoms
Organic & Inorganic Polymer

Inorganic Polymers
 Polymers whose back bone chain is not having C- atoms.
 Mostly Inorganic polymers contains the elements of IV-VI
groups i.e Si, Ge,P, S, Se etc.
Examples: (i) Polysilane
H H H H H H

- Si - Si - Si - Si - Si - Si -
H H H H H H

Rhombohedral ∆
Sulphur -S-S-S-S-S-S-S-S-
S8
Types of Atoms
Organic & Inorganic Polymer
Organic polymers
 Polymer whose backbone chain is essentially made of
carbon atoms.
 Examples: Synthetic and Natural polymers like PE, PP,
Nylon, starch, cellulose etc.
Number of monomer
Homopolymer & Copolymer

Homo polymer
 Polymer formed from a single monomer unit.

Examples:

CH2 CH2 CH2 CH

n
CN
n
PTFE Polyethylene (PE)
Or Teflon PAN
Polyacrylonitrile
Number of monomer
Homopolymer & Copolymer
Copolymer
 Polymer is formed from two or more different monomer
units. Two or more repeat units are present.

A copolymer is again classified into 4 types

 Random : A-A-B-A-B-B-B-A-A-A
 Alternate : - A - B - A - B - A - B - A - B - A - B -
 Block : - A - A - A - B - B - B - A - A - A -
 Graft : -A-A-A-A-A-A-A-A-A-
B B
B B
B
Structure/Shape
Linear, Branched or Cross-linked

Polymer Structure
 Linear : The monomers linked together to form a linear chain.

Examples: Nylon, Polyester, High density PE

 Branched: The monomers linked together in such a manner to

form branched structure.

Examples: Starch, Glycogen, Low density PE

 Cross-Linked: Linear chain having two or more reactive sides

linked together to form network structure.

Examples: Phenol-formaldehyde (Bakelite),

Urea-formaldehyde resins etc.

Structure/Shape
Linear, Branched or Cross-linked

1. Linear polymers 2. Branched chain polymers

Eg: Polyethylene Eg: Polyethylenimine

3. Three dimensional network

(branched) polymers.

Eg: Phenol-formaldehyde resin (Bakelite)

Structure/Shape
Linear, Branched or Cross-linked

Polymer structure

+O O
Bifunctional Monomers Linear polymer

O
+
O O
Trifunctional Bifunctional Branched polymer Cross-linked
End use
Fibers, Plastics and Elastomers

Elastomers
 Elastomers have the tendency to return back to their original
shape after releasing of external stress.

 Molecules in elastomers have weak intermolecular force of

attraction.

 Some degree of crosslinking is needed for the rapid and

elastic deformation.

 They posses little or no crystallinity.

 Example-Polyisoprene (natural rubber)

 Extensive crosslinking of a rubber converts the polymer to a

rigid plastic.

 An automobile tire requires much more crosslinking and

reinforcing fillers than the elastomer used for producing

rubber bands.
End use
Fibers, Plastics and Elastomers
Fibers
Very high resistance to deformation.
Very highly crystalline and contain polar chains with strong
secondary forces.
Tm should be high (200-3000C). (Tm = melting temperature)
Tg should have an intermediate value. (Tg = glass transition
temperature)
Example- Poly(hexamethylene adipamide) [nylon-6,6]
Note: Polypropene used as a fiber has a highly stereoregular
structure.

nylon-6,6
End use
Fibers, Plastics and Elastomers
Plastics
 Plastics have a wide range of mechanical behaviors in
between those of the elastomers and fibers.
 There are two types of plastics—flexible plastics and rigid
plastics. Rigid plastics
Flexible plastics  high rigidity, resistance to
 moderate to high degrees of deformation, high young’s moduli
crystallinity and a wide range & Tg values
of Tm and Tg values.  moderate to high tensile
 moderate to high moduli, strengths & undergo very small
tensile strengths, and elongations before rupturing
ultimate elongations.  Example- phenol–formaldehyde,
 Example- polyethylene, urea–formaldehyde, and
polypropene & melamine–formaldehyde
poly(hexamethylene polymers, polystyrene and
adipamide) (Nylon-6,6) poly(methyl methacrylate

Nylon-6,6
polypropene
Physical state
Crystalline and Amorphous polymers

Amorphous polymer
 Polymer chains with branches or irregular pendant groups
cannot pack together in a regular order, they are called
amorphous polymer.

 The molecules of an amorphous polymer are oriented randomly

and are intertwined.

 Show only short range order & are transparent.

 Lower density than crystalline polymers.

 Examples: LDPE (low density polyethylene), conventional PS,

PMMA etc.
Physical state
Crystalline and Amorphous polymers

Crystalline polymers
 Molecules or chains are arranged in a regular pattern.
 They are rigid, have a high melting point, and are less
affected by solvent penetration than amorphous polymers.
Examples: HDPE, PET

Packing of molecular chains to produce

an ordered atomic array
Unit cells are often very complex

Orthorhombic geometry

The crystallinity of a polymer range from

purely amorphous to almost entirely
crystalline (~95%)

Unit cell of polyethylene

Physical state
Crystalline and Amorphous polymers

Crystalline polymers
The degree of crystallinity of a polymer is
influenced by

 Molecular weight
 Symmetry of repeating unit
 Chain Branching
 The rate of cooling during solidification
 Polymer Crystallinity

 Linear polymer can easily crystallize.

 In branched polymer, crystallization is prevented.
 Most Network and crosslinked polymers are totally amorphous.
 Atectic polymers are difficult to crystallize.
 Isotectic and syndiotectic polymers are more easily crystallize.
 Bulkier the side groups of a polymer, less tendency for it to crystallize.
 For copolymers, alternating and block polymers have greater
tendency for the development of crystallinity as compared to random
and graft copolymers
Physical state
Crystalline and Amorphous polymers

Semicrystalline polymer
 A semicrystalline polymer consists of small crystalline regions
(crystallites) interspersed with amorphous region composed
off randomly oriented molecules.
Stereochemistry
Isotactic, Syndiotactic & Atactic
Stereoisomerism
 Same order in atomic links but differ in the spatial
arrangement of the atoms or groups

Isotactic configuration: The R groups are situated in

the same side of the chain

H H H H
H R R R
R
R
C C C C C
C C C C
C
H H H H H
H H H H
H

R H R H R H R H R H
CH2 - CH
-C-C-C-C-C-C-C-C-C-C-
R H H H H H H H H H H
n
Stereochemistry
Isotactic, Syndiotactic & Atactic

Syndiotectic configuration: The R group alternates

H H R R H R H side of the chain
H R
R
C C C C C
C C C C
C
H H H H H
H H H H
H
R H H H R H H H R H
-C-C-C-C-C-C-C-C-C-C-
H H R H H H R H H H

Atactic configuration: The R group are placed randomly

H R H R
H R H R H
R
C C C C C
C C C C
C
H H H H H
H H H H
H
 Plastics
 Plastics are organic materials of high molecular weight which
can be moulded into any desired shape when subjected to
heat and pressure.
 The word Plastic came from a Greek word 'plastikos' and
'plastos' which means 'fit for moulding' and 'moulded’.
 Plastics are of two types, Thermoplastics & Thermosets

 Examples: PE, PS, PVC, Teflon etc.

Polymer Plastic
Definition Large molecules that has It is a polymer that has large
same structural repeat unit molecular mass
Nature Can be either natural or A synthetic polymer
synthetic
Structure Linear, complex and Mostly linear
branched
 Properties of Plastics
 Light in weight
 Good thermal and Electrical Insulator
 Corrosion resistant and Chemically Inert
 They have good strength, dimensional stability and
toughness.
 Easy moulding.
 Low softening point.
 Transparency: Some plastics are highly transparent

Disadvantages
 Combustibility  Deforms under applied
 Poor ductility load
 Softness  Low thermal stability
 High cost
 Thermoplastics
 They are polymers which soften on heating and harden on
cooling.

 They have either linear or branched structure.

 Neighboring polymer chains are held together by weak Van

Der Waals’ force and hydrogen bonding.

 They can be remolded, reshaped or reused & hence reclaimed

from the waste,

 They are soft & soluble in organic solvent

 Example: PP, PMMA, PVA, PS

PVA
 Thermosets
 They are polymers which on heating undergo chemical
changes and convert themselves into infusible & insoluble
mass.

 They have three dimensional, cross linked network structure.

 Neighboring polymer chain in thermosets are held together

by strong covalent bond.

 They can’t be remolded, reused and reshaped and

reclaimed.

 Examples; Bakelite, Epoxy resin, amino resin.

 Thermoplastics

1. Polyethylene
1000 – 5000 atm
n CH2 = CH2 CH2 – CH2
250 0 C, O n
Ethylene 2
LDPE
Branched Structure
Properties
 Density and Crystallinity is low
 It is rigid and nonpolar material
 Chemically inert
 Good Insulator
 Mechanism
Polyethylene
 Ethylene is a gas at ambient temperature and pressure
 Ethylene gas is subjected catalytically to appropriate
conditions of temperature and pressure

Initiation I 2R
Initiator Free radicals
H H H H
. + .
R C C R C C

H H
H H
Propagation

H H H H H H
H H

R C
. .
C + C C R C C C C

H H H H H
H H H
H H H H
R-C-C R - .C - C H
Termination H H H

H H H H H H H H H H H H

2 . R C C C C C C C R
R C C C C C

H H H H H H H H H H
H H
 Polyethylene

Zeigler – Natta
n CH2 = CH2 CH2 – CH2
TiCl4-Al(C2H5)3 n
Ethylene
60-700 C, 6 - 7 atm HDPE
Linear Structure
Properties
 Density is high and more crystalline nature
 It is more stiff, hard and greater tensile strength
as compared to LDPE
Uses
Carry bags, film, packaging materials, mugs,
toys, ink tube for pen
 Mechanism
TiCl4 + Al (C2H5)3 (C2H5)2 Al Cl + (C2H5)TiCl3

 
+
Cl Cl C2H5
+
Cl Cl C2H5
+ +
Ti  Al Ti  Al
 
Cl H2C C2H5
Cl CH C2H5

CH3
CH3 H2C C R
H

+
Cl Cl C2H5
+

Ti Al

Cl CH C2H5

CH2R C CH3
H2
 Polyvinyl chloride (PVC)

Benzoyl peroxide
n CH = CH
2 / H2O2 CH2 - CH
n
Vinyl Chloride Cl
PVC Cl
Properties
 It is colorless, odorless and chemically inert powder
 It is resistant to light, Inorganic acid & Alkali
 Soluble in chlorinated hydrocarbon and THF
 High softening point, greater stiffness and rigidity as
compared to PE but it is brittle.

It is most widely used synthetic plastics. Used

USES for making sheets, safety helmet, drainage pipe,
bottle for edible oil, mineral water bottle, rain coat.
 Polystyrene (PS)
CH CH2
CH-CH2
Benzoylperoxide
n n

Styrene PS
Properties
 It is transparent, light & moisture resistant polymer
 It is hard but brittle in nature.
 It is an amorphous polymer.
 Softening temp is low (82-1000 C).

Uses Bottle caps, Audio cassettes, comb and brush

handles, jars, storage container
 Polymetylmethacrylate (PMMA)
CH2 = C - COOCH3 COOCH3

CH3 CH2 - C

Methyl methacrylate CH3

n
Properties PMMA
 It is amorphous, colorless & transparent
 thermoplastic with high optical transparency
 It is hard but become rubber like above 650 C
 Low chemical and scratch resistance

Uses: Making lens, optical fibers, aircraft light fixture, window

and TV screens
 Teflon
F F F F

n C C C C
Benzoylperoxide
n
F F F F

Tetraflouroethylene PTFE/Teflon

Properties
 Excellent toughness and heat resistance
 Exceptionally high chemical resistance
 Good electrical insulator and non adhesive
 High softening temperature
 Teflon
 It can’t be dissolved or can’t be exist as a true molten
stage.
 Due to chemical inertness & high temp softening, it
behaves like a thermoset.
Uses:
 Coating of frying pans (non-stick pan)
 Variety of seals, gaskets, packing valve, pump parts,
stop cork for burette.
 Thermosets
 They become permanently hard during their formation and
does not soften during heating.
 Mostly they are crosslinked and 3-D network polymers.
 These polymers have covalent crosslink structure between the
molecular chains and hence resist vibrational and rotational
motion at high temperature.
 Thermoset polymers are harder and stronger than the
thermoplastics.
 Ex. Epoxies, Phenolics and Amino resins
 Phenolic resins
These are condensation product of phenol and formaldehyde, in
presence of acid or alkyl catalyst. It is also known as bakelite
(PF resin)

-
OH
 Phenolic resin
I. Case 1
In presence of acid catalyst and with mole ratio of
Phenol/Formaldehyde > 1, the methylol derivatives condense
with phenol to give low molecular weight linear polymers, that
are fusible and soluble and is known as NOVOLAC.

Three dimensional cross linked polymer are obtained either

by heating the linear polymer chain with one of the monomers
or with other reagents by a process called curing.
 Phenolic resin
OH OH OH

CH2OH H H HOH2C

+ +

H+ - H2O

OH OH OH
H2 H2
C C

NOVOLAC
 Phenol-Formaldehyde resin
OH OH OH
H2 H2
C C
(CH2)6N4
Hexamethylene
tetraamine
NOVOLAC OH OH OH
H2 H2
C C

CH2 CH2 CH2

Bakelite C
H2
C
H2
OH OH OH
 PF Resin
II. Case 2
In presence of alkaline catalyst and when P/F < 1, the
methylol phenols can condense either through methylene
linkage or through ether linkage to form resoles. Heating
resoles Cross linked product formed known as resite.
OH OH

CH2OH HOH2C CH2OH

+
OH-

OH OH

HOH2C H2C CH2OH

OH OH

HOH2C CH2O H2C CH2OH

Resoles
 Phenolic resin

Properties Uses
 Rigid, hard and strong  Electric plugs, switches and
materials switch board
 Excellent heat, moisture and  Handle of cookers
chemical resistance
 Impregnating fabrics, wood
 Good electrical insulator paper
 Excellent bonding strength  Adhesives for grinding
and adhesive properties wheels and brake lining
 Amino resin
They are prepared by condensation reaction of
formaldehyde with urea or melamine to give urea -
formaldehyde or melamine formaldehyde resin.

Urea-formaldehyde resin O
NH2
NH2 C NH CH2OH
H2N HCHO monomethylol urea
OH- +
O O
urea
HOCH2 NH C NH CH2OH
dimethylol urea
 UF Resin
Methylol derivatives undergoes further condensation reaction to
form cross-linked polymer

H N CH2OH H N CH2OH

C O + C O

H N CH2OH H N CH2OH

N CH2 N CH2 N

C O C O C O

N CH2 N CH2 N
Urea-Formaldehyde
 UF resin

Properties Uses

 Better hardness & Tensile  Adhesive for plywood and

strength than PF furniture
 Good solvent, grease and  Finishing of cotton textile
moisture resistance  Making button, vaccum
 Good adhesive flask cups & Jugs
characteristics
 Melamine-Formaldehyde
MF resins are prepared by heating melamine with
formaldehyde in alkaline medium to form methyl melamine and
low molecular intermediates.
NH CH2OH

NH2 N Di-methylol
N H2N N melamine
OH-
N
H2N N
NH CH2OH
N
NH CH2OH
NH2
N
Melamine Tri-methylol
HOH2C HN N
melamine
N

NH CH2OH
 MF resin
NH
HN-H2C N NH CH2 - NH -
NH CH2OH

H2N N N N
N
Excess HCHO
NH CH2OH
NH
∆
+ CH2
NH CH2OH
NH
N

HOH2C HN N

N N N
NH CH2OH

-NH- CH2 HN N NH CH2-NH -

Cross-linked MF resin
 MF resin
Properties Uses
 Good resistance to heat, water  Cellulose filled MF resin used
and chemicals for high quality dinner wares.
 Compared to UF, MF has better  Used for production of
hardness, heat and moisture decorative laminates for
resistance. furniture.
 They have good adhesive  Used in plywood industry as
characteristics which are boil adhesive
resistant.  Textile finishing agent
 Epoxy resin (Araldite)
 They are prepared by condensation reaction between
bisphenol and epichlorohydrin.

CH3

OH +
Cl CH2 CH CH2
HO C
O
CH3
Epichlorohydrin

Bisphenol A OH-

CH3
O C O CH2 CH CH2
CH3 OH
n
 Epoxy resin
Low molecular weight polymer with epoxy groups at its
end forms cross linked structure by adding diamine or
dianhydride.

Properties

 Low water absorption capacity, good electrical and heat

insulator.
Uses:
 They used as adhesive for glass, metals etc.
 Skid resistance surface of highway.
Difference between thermoplastics and thermosetting
plastics
Sl. No. Property Thermoplastics Thermosetting plastics
1 Action of heat Soften on heating and set on Set on heating and cannot be
cooling resoftened

2 Process Reversible Irreversible

3 Type of change Physical change Chemical change
4 Type of bonding Polymer chains are held together The polymer chains are linked by
between adjacent by weak force called Vander strong chemical bonds (covalent
polymer chains Waal’s force of attraction bonds)

5 Solubility Soluble in organic solvents Insoluble in organic solvents

6 Expansion due to They expand very much on Their expansion is only
heating heating marginally on heating

7 Type of Formed by addition Formed by condensation

polymerization polymerization polymerization

8 Scrap recovery Scrap can be reused Scrap cannot be reused

9 Type of moulding Processed by injection moulding Processed by compression

moulding
 Adhesive
Adhesive or glue is a compound in a liquid or semi-liquid
state that adheres or bonds items together.

Adhesives may come from either natural or

synthetic sources

Natural adhesive: Starch/dextrin, casein

Synthetic adhesive: epoxy, polyurethane,thermoplastics
Adhesive -
O

Cyanoacrylate
N
 Fibers
 They are materials thin, long and thread like structure.
They have greater tensile strength in the direction of
fiber.

Fibers are classified into three classes.

 Natural fibers: Wool, Silk, cellulose, Jute
 Semi-synthetic fibers: Cellulose acetate, cellulose
nitrate etc.
 Synthetic fibers: Nylons, polyesters, acrylic fibers
 Properties

 High tensile strength

 Synthetic fibers are durable as compared to natural
fibers
 Superior abrasion resistance
 Nylons
NH2 - (CH2)6 - NH2 + HOOC - (CH2)4 - COOH
Adipic acid O
NH - (CH2)6 - NH - C- (CH2)4 - C

Nylon 6,6 O
n
NH2 - (CH2)6 - NH2 + HOOC - (CH2)8 - COOH
Sebacic acid
O
NH - (CH2)6 - NH - C- (CH2)8 - C
O
Nylon 6,10 n
+ HCN NC- (CH2)4 - CN
1, 3 butadiene

NH2 - (CH2)6 - NH2 HOOC - (CH2)4 - COOH

 Nylon 6
NH H O
N - (CH2)5 - C
O
n

Caprolactam

C O
(CH2)5
NH2 - (CH2)5 - COOH
NH
H2O
Amino acid initiate the polymerization process
 Nylons

 They are linear and highly

crystalline polymer
 High melting point, toughness
and abrasion resistance.
 Molecular chains are held
together by hydrogen bonds

Uses: making fibers

 Terylene (PET)
H H O O
HO C C OH + HO C C OH
H H O
H H O
Terephthalic acid C
Ethylene O C C O C
Glycol n
H H + H2O
PET
 It is linear and crystalline polymer
 It has good resistance to hydrocarbon solvents and moisture
 They are more durable and low moisture absorbing fiber
forming materials

Uses: Magnetic recording tape, Transparency, soft drinks bottle

 Polyacrylonitrile (Orlon)
CH2 CH CH2 - CH
n
CN CN
Acrylonitrile PAN

 They have high softening point (3000 C)

 They dissolved in DMF
 Orlon fibers are resistant to water

Uses: Wool like fibers for bathing suits, sweater etc..

 Elastomers
 Elastomers are High molecular weight polymers that exhibit
rubber-like behavior.
 They have the tendency to return back to their original shape
after releasing of external stress & posses little or no
crystallinity.
 Molecules in elastomers have weak intermolecular force of
attraction.
 Example- Rubbers are lightly cross-linked amorphous
materials.
 Natural Rubber
Natural rubber is polymer of Isoprene unit(C5H8)n

Isoprene Polyisoprene
(C5H8) (C5H8)n
 Natural Rubber

H3C H
H3C H2C
C C
C C
CH2 H2C
CH2 H
Cis-polyisoprene
Trans-polyisoprene
(CH3 and H are in the same
(CH3 and H are on the opposite
side of the double bond)
side of the double bond)
Natural Rubber Gutta Percha
 Natural rubber

H3C H H3C H
H3C CH2
C C C C
C C
CH2 CH2 C H2C
H CH3 H2

Structure of Natural rubber

cis-polyisoprene
 Rubber processing

Rubber latex: milky liquid rubber obtained

from rubber tree.

Rubber filtration Dirt free

Diluted
Latex latex latex

Coagulation

Acid free Washing

Coagulated Coagulated
rubber rubber
 Vulcanization

Raw Rubber Sulphur Cross-linked

100-1400 C structure
H3C H H3C H
H3C CH2 S
C C C C
C C ∆
CH2 CH2 C H2C
H CH3 H2

CH3 H CH3 H

C C C CH2 CH2 C C CH2

H2
S S S S

C C C CH2 CH2 C C CH2

H2
Vulcanized Rubber CH3 H CH3 H
 Advantages

 Tensile strength is very good, about 10 times than the raw

rubber.

 Broader useful temperature (~ 40 – 1000 C) as compared to

raw rubber (~ 10 – 600 C)

 Better resistance to moisture, oxidation & abrasion

 Synthetic rubbers
Neoprene:
It is prepared by free radical polymerization of
chloroprene.
H2O2
CH2
CH CH2
C

Cl CH2
CH2
2-Chloro 1,3 butadiene
C C
This can be vulcanized to a H
Cl
considerable extent by applying heat n
Neoprene
Uses: shoe soles, adhesive, gloves, gaskets, cable/wire insulators
 Butyl rubber
CH3 H3C

H2C C + C C AlCl3
CH3 H2C CH2 ∆

Isobutene Isoprene
CH3
 Soluble in hydrocarbon
CH2 C CH2 C CH CH2
solvent like benzene
 degraded to low mol wt CH3 CH3
Product by heat and light n
Butyl rubber
Uses: Inner tubes of automobile, insulation for high
voltage wires/cable
 Styrene rubber (Buna-S), SBR
It is prepared by co-polymerization of styrene and butadiene in
an emulsion system at 500 C in presence of free radical initiator.

CH CH2
CH2 H2O2
CH2 C CH
H
CH CH2 CH C CH2
+ H
n

 It can be vulcanized like natural

rubber by reaction with sulphur. Buna-S
 They have high load bearing capacity

Uses: motor tyres, foot wear components

 Polyurethanes
They are prepared by polymerization of diisocyanates with
dihydric alcohols

O C N (CH2)6 N C O + OH
HO
Di-isocyanate
diol

O O

C NH (CH2)6 NH C O (CH2)6 O

Polyurethane n

PU-Thermosetting
polymer
 PU polymer
Less stable as compared to Nylon
High resistance to oxidation

Uses: used as elastomers, foams, fibers

General methods of preparation

1. Addition or chain polymerization

2. Condensation or step polymerization

3. Ionic polymerization

4. Co-polymerization
 Addition or chain polymerization
Monomers combine together to form polymer without losing any atom or
molecule. Here the polymer is the exact multiple of the monomer.
Eg: polyethylene, polystyrene.
1. Initiation:
=
R∙
2. Chain propagation:
Condensation or step polymerization
Monomers combine together to form polymer with losing small
molecules like water or HCl by condensation.

Eg: Polyethylene terephthalate (Nylon 6:6).

Nylon
 Ionic polymerization
a. Cationic polymerization:
Polymerization initiated by a Lewis acid.
Eg: Polymerization of styrene

1. Initiation:

2. Chain propagation:

3. Chain termination:
b. Anionic polymerization
Polymerization initiated by a Lewis base.

Polymerization of methylmethacrylate
1. Initiation:

2. Chain propagation:

3. Chain termination:
 Copolymerization
Polymerization among monomers of two different chemical
substances form Copolymer.

Homopolymer

Regular copolymer

Random copolymer

Block copolymer

Eg: Polybutadiene-co-styrene (Styrene – butadiene rubber)

Properties of polymer
 Criteria for polymer solubility
The Solution Process
 Dissolving a polymer is a slow process & occurs in two stages.
 1st stage- Solvent molecules slowly diffuse into the polymer to produce a
swollen gel. This may be all that happens if, the polymer-polymer
intermolecular forces are high because of crosslinking, crystallinity, or
strong hydrogen bonding.
 2nd stage- Strong polymer solvent interactions overcome strong polymer-
polymer intermolecular forces, resulting in solution. Here the gel gradually
disintegrates into a true solution.
 Polymer Texture and Solubility
 Solubility relations in polymer systems are more complex
than those among low-molecular-weight compounds.
Because of the size differences between polymer and
solvent molecules, the viscosity of the system, and the
effects of the texture and molecular weight of the polymer.

 The presence or absence of solubility as conditions (such as

the nature of the solvent, or the temperature) are varied can
give much information about the polymer; this is in fact the
topic of most of this chapter.

 Crosslinked polymers do not dissolve, but only swell if they

interact with the solvent.
 Conformations of dissolved polymer chains

 Arrangements of the polymer chain differing by reason of

rotations about single bonds are termed conformations.

 The size of the molecular coil is very much influenced by the

polymer-solvent interaction forces.

 In a thermodynamically "good" solvent the coils are relatively

extended (polymer-solvent contacts are highly favored) & In a
"poor" solvent they are relatively contracted.
 Entropy and Heat of Mixing of Polymer
Solutions
 Deviations From Ideal Behavior. Polymer solutions

invariably exhibit large deviations from Raoult's law, except

at extreme dilutions.

 Entropy of Mixing. Deviations from ideality in polymer

solutions arise largely from small entropies of mixing.

 Heat and Free Energy of Mixing. The heat of mixing of'

polymer solutions is analogous to that of ordinary solutions.

Phase equilibrium in polymer solutions
Polymer-Solvent Miscibility

When the temperature of a polymer solution is raised or

lowered a temperature is reached beyond which polymer
and solvent are no longer miscible & the mixture
separates into two phases.
Phase separation may also be brought about by adding a
nonsolvent liquid to the solution.
The maximum temperature for phase separation is the
upper critical solution temperature.
Phase separation occurs also when the temperature is
raised until a lower critical solution temperature is
reached.
 Thermal Transitions
 Two types of transition temperatures are the
crystalline melting temperature Tm and the glass
transition temperature Tg .

Tm: Tg:
 characteristic  characteristic properties of
properties of the amorphous domains of a
crystalline domains polymer
of a polymer  Tg is a second-order
 Tm is a first-order transition
transition

 amorphous polymers show only a Tg, crystalline

polymer shows only a Tm, Semicrystalline polymers
exhibit both the crystalline melting & glass transition
temperatures
Fig. Determination of Tg and Tm by changes in specific
volume
 The most commonly used method is differential
scanning calorimetry (DSC)

 polymers undergo other thermal transitions like crystal–

crystal transitions and crystalline-liquid crystal
transitions.
 Factors affecting glass transition
temperature
 Tg depends on the molecular weight of the polymer,
pressure, tacticity, cis and trans isomerism, entanglement
etc.
 Flory-Fox equation (an empirical equation)
Tg(Mn) ≈ Tg,∞ - K / Mn

Where, Tg,∞ = limiting value of Tg at very high mol. Wt.

Mn =number-average molecular weight
K= constant for a given polymer that is related to
the free volume present in the polymer.
 Tg increases with the molecular weight and reaches a
limiting value at moderate to high molecular weights.
Influence of structure of polymer on its
properties
Strength of polymer
 Crosslinked polymer are strong & tough as the
intermolecular chains are totally restricted.
 Straight chain polymer having
low [Link].-soft and brittle
higher chain length- tougher & more heat
resistance
 Presence of polar groups increases the intermolecular
forces & strength of polymer.

Plastic deformation
 linear chain polymers soluble in solvent & thermoplastic
 3D polymer molecule are thermosets & insoluble
 crosslinking converts thermoplastic material into
thermosetting
114
Physical state
 Amorphous - random arrangement of molecules, provides
flexibility.
 Crystalline - regular arrangement of molecules, results in
higher softening point, greater rigidity, brittleness & strength
of polymers.
 Elastic character- free rotating groups in long chain
polymers form irregular coiled and entangled snorts
Solubility and chemical resistance
 presence of polar groups – soluble on polar solvents
 Presence of non-polar groups- soluble in non-polar solvent
 Cross-linking decreases the solubility
Shape and forms—mechanical properties
 The internal arrangement of long chain molecules provide the
form of polymer, i.e. fibres, plastic & rubber
 Rubbery character is due to low internal forces between
molecule & random arrangement
 Fibrous nature forms as a result of high internal forces and
orderly arrangement
Effect of heat
 Amorphous polymer becomes rubbery and then gummy on
heating above Tg. But the crystalline polymer on heating above
Tg shows thermoplastic behaviour and finally liquefies.
 Molecular weight
 The polymerization process results in mixture of polymers
that vary in chain length. Therefore, a statistical average
molecular weight is used for characterization.
 The average molecular weight can be expressed in two
ways, number average and weight average.

Number average mol. wt.- It is the sum of all molecular

weights divided by their total number.

where, N= total no. of molecules,

Ni=no. of molecules having a mol. Wt. Mi,
wi = weight fraction of all molecules having a mol. Wt. Mi.
Weight/ Mass average mol. wt.- It is the sum of all
molecular weights multiplied by their weight fractions (wi):

The two expressions for the average molecular weight are

special cases of the general expression for weight averages:

The parameter α is the so-called weighting factor, which

defines the particular average.
Mm = Mw

119
The ratio of weight and number molecular weight is called
the polydispersity index. It is a measure for the
broadness of a molecular weight distribution of a polymer.

 In the case of solution viscosity, the weight dependence

of the viscosity can be described by the well-known
empirical Mark-Houwink (1940) relation:
[η] = K Mα

where [η] = intrinsic viscosity,

α, K =Mark-Houwink parameters.
Measurements of the viscosity yields the viscosity average
molar weight:
Effect of molecular weight, dispersity and branching
on polymer properties
Higher molecular weight improves the mechanical
properties,i.e., break, yield, and impact strength increase.
It increases the Tm and Tg as well as the solution and melt
viscosity which makes processing and forming of the
polymeric material more difficult.

lower dispersity (narrower distribution) leads to better

mechanical properties
branching lowers the mechanical properties
 Mechanical Properties
 Mechanical behavior, i.e., deformation and flow
characteristics under stress determines the general utility of
a polymer .
 Characterized by its stress–strain properties.
 This often involves observing the behaviors of a polymer as
one applies tension stress to it in order to elongate (strain) it
to the point where it ruptures (pulls apart).
 The results are usually shown as a plot of the stress versus
elongation (strain).
 The strain can also be expressed as the percent elongation,
L=L 100%.
 Four important quantities characterize the stress–strain
behavior of a polymer:

1. Modulus. The resistance to deformation as measured by

the initial stress divided by L=L.

2. Ultimate Strength or Tensile Strength. The stress required

to rupture the sample.

3. Ultimate Elongation. The extent of elongation at the point

where the sample ruptures.

4. Elastic Elongation. The elasticity as measured by the

extent of reversible elongation.
  Mechanical behavior
depends on the degree of

Stress
crystallinity, degree of
crosslinking, and the values
of Tg and Tm.
 High strength and low
extensibility are obtained in
polymers by having various
combinations of high
degrees of crystallinity or
crosslinking or rigid chains
(characterized by high Tg).
Strain

 High extensibility and low strength in polymers are synonymous with low degrees of
crystallinity and crosslinking and low Tg values.
 Strength is lost at or near Tg for an amorphous polymer and at or near Tm for a
crystalline polymer.
125
 Optical properties of polymers
 Optical properties means how the material interacts with light.
 There are three key interactions between light and polymers
[Link] (for clarity)
[Link]
[Link]
 Transmittance is defined as the ratio of light intensity passing
through the material to the intensity of light received (or
absorbed) by the specimen & determined
by reflection, absorption and scattering.
 Reflectivity is the fraction of incident light intensity reflected
at the interface (surface effect).
 The optical properties of polymers, including gloss, and
transparency, are critical to many applications of
commercial plastics.

 Gloss is an optical property which describes how well a

surface reflects light in specular direction.

 If both absorption and scattering are negligible, the material

is called transparent.
The optical appearance is determined by surface
texture, porosity, degree of crystallinity, and crystal size
and structure.

The lustrous appearance of a plastics is determined by

reflection and diffraction.

If the reflectance is almost zero, the surface appears

totally matt whereas highly polished (smooth) surfaces
have high reflectance and appear shiny to the eye.

Most common polymers are clear and colorless

because they do not (selectively) absorb light in the
visible spectrum.
 Polymer clarity
Amorphous polymers are transparent and increasing
crystallinity leads to translucency. This is because polymer
crystals scatter light.

Most common optically clear polymers are acrylics,

polycarbonates, and polystyrene which form amorphous
structures.

An exception is PET which is clear and [Link]

this case the crystals are much larger than wavelength.
 Electrical properties of polymers
 Based on the presence of conjugated double bonds
(alternating single and double bonds ) along the polymer
backbone.

 Through doping process, charge defects (polaron) are

created that can travel through the backbone of the polymer,
or to be more specific, through the conduction band.
 The first polymer with significant conductivity synthesized
was polyacetylene (polyethyne).
 The conductivity of polyacetylene is due to the existence of a
conducting band similar to a metal.
 Intrinsically conducting polymers generally have conjugated
bonds or composed of aromatic rings such as phenylene,
naphthalene, anthracene, pyrrole, and thiophene which are
connected to one another through carbon-carbon single bonds.
ELECTRICAL CONDUCTIVITY OF SOME CONDUCTIVE POLYMERS
Compound Repeating Unit Conductivity (S cm-1)

trans-Polyacetylene 103 - 105

Polythiophene 103

Polypyrrole 102 - 7.5 · 103

Poly(p-phenylene) 102 - 103

Polyaniline 2 · 102

Poly(p-phenylene vinylene) 2 · 104

 The conductivity of conducting polymers increases with
temperature.
 Doping increases the conductivity by many orders of
magnitude .
 mechanical alignment of the polymer chains increase
conductivity . The actual conductivity depends on the
structure, morphology of the polymer, type of dopant and its
concentration.
 Rheology
 Rheology is the science of deformation and flow of matter.

 The rheological behavior of polymers involves several widely

different phenomena, which can be related to some extent to
different molecular mechanisms. These phenomena and their
associated major mechanisms are follows:

1. Viscous flow, the irreversible bulk deformation of polymeric

material, associated with irreversible slippage of molecular
chains past one another.

2. Rubberlike elasticity, where the local freedom of motion

associated with small-scale movement of chain segments is
retained, but large-scale movement (flow) is prevented by the
restraint of a diffuse network structure.
[Link], where deformation of polymer specimen is
reversible but time dependent and associated (as in rubber
elasticity) with the distortion of polymer chains from their
equilibrium conformations through activated segment motion
involving rotation about chemical bonds.

[Link] elasticity, where the motion of chain segments is

drastically restricted and probably involves only bond
stretching and bond angle deformation; The material behaves
like a glass.
Characterization
Measurement of molecular weight and
size
 The molecular weights of polymers can be determined
by chemical or physical methods of functional-group
analysis, by measurement of the colligative properties,
light scattering, or ultracentrifugation, or by
measurement of dilute-solution viscosity.
 All these methods except the last are, in principle,
absolute: Molecular weights can be calculated without
reference to calibration by another method.
 Degradation of polymer
 It implies a decrease in chain length or molecular weight.

 For all practical applications, it is the objective and desire

that the polymer perform up to expectation and in tune with
its potential without degradation due to various agencies
inherent or given rise to its environment such as heat, light
(or other radiation), atmospheric oxygen, moisture, acid,
alkali or other chemicals, mechanical force, microorganisms
etc.
 The degradation process can be prevented or delayed with the

use of additives.

 Example – When the role of O2 is recognized in the degradation

of polymer, the relevance and importance of antioxidant

additives can be better realised and appreciated.

 Recycling
 To aid in the separation of various types of plastics , a
recycling symbol is placed to indicate the type of plastic.
 The symbols consist of three arrows around one of seven
numbers; an abbreviation below the symbol indicates the
type of polymer from which the container is made.
 The lower the number in the middle of the symbol, the
greater is the ease with which the material can be recycled.
1 for poly(ethylene terephthalate),

2 for high-density poly-ethylene,

3 for poly (vinyl chloride),

4 for low-density polyethylene,

5 for polypropylene,

6 for polystyrene, and

7 for all othe plastics.

List of some important polymers and
their applications in day to day life.
1. Polyethylene:
Packaging, plastic bottles, and plastic bags.

2. Polyvinyl chloride:
pipes, window, door frames, water proof fabric, electronic wire
insulators, home appliances.

3. polystyrene:
CD cases, petri dishes, Styrofoam packaging material, food
and water containers.
4. Polyacrylamide:
water purifier, paper coating, cosmetic additive, photographic
emulsion, contact lenses.

5. polyurethane: packaging foam, paint, adhesive.

6. Polytetrafluoroethylene: hydrophobic coatings on cooking

utensils, chemical resistant coatings, .
7. polycarbonate:
Bullet proof glass, sun glasses, CD, DVD etc.

8. polyacetylene: semiconducting materials.

9. Polystyrenesulfonic acid:
Water purification systems, Ion exchange devises.

10. poly(p-phenylene vinylene):

Electroluminescence, LED display devices.
11. Nylon, cotton: Cloths, fabrics, ropes.

Nylon