~

1.60 ENGII'!EERING CHEMISTRY

7. Explain in detail with a neat diagram, softening of water UNIT · II

by lime-soda method.
~ Explain with a neat sleetch, desatination by POLYMER CHEMISTRY
electrodialysis.

11 9. A sample water on analysis gave the following results: Related Terminology - Types of Polymers - Polymerisation Types -
Ca(HC03)2 = 324 ppm ; Mg(HC03)2 = 292 ppm; Mechanism of Polymerization (Free Radical Mechanism / Ionic /
Co-ordination) - Thermoplastics & Thermosetting Plastics (PE,
CaS04 = 68 ppm; CaCl2 = 111 ppm; MgCl2 = 95 ppm.
PVC, Bakelite and epoxy resins - preparation, properties and
Find the amount of lime (90% pure) and soda (93% pure) applications - Effect of Polymer Structure on Properties -
required for softening 50000 litres of water. Compounding of Plastics - Molding Methods (Compression molding
and injection molding) - Polymer Composites, Blends, LCP:' -
Definition, Examples and uses.

II
*** 2.1 IINTRODUCTION

Polymers are macromolecules posessing high

molecular weight and are formed by the linking of a large
number of simple molecules called monomers. Such
molecules exists in nature. (e.g.,) Starch, cellulose, silk, wool,
leather, rubber etc. The polymer molecules can also be
produced by synthetic methods. Some such synthetic polymers
are polyethylene, (PE), Polyvinyl chloride (PVC), nylon,
pterylene, bakelite etc.,

The polymer molecules possess excellent physical and

chemical properties. It is note worthy to mention here that
these molecules possess good corrosion resistance, toughness,
high mechanical strength, optical properties, durability, rigidity
etc., Due to these properties, polymers act as substitute for S

conventional materials such as iron, wood, glass etc., Hence

the field of polymer chemistry gains more and more
significance in the current research inspite of the problems
faced due to its non-biodegradability. In this context, jt
;0 /.
2.2 ENGINEERING CHEMISTRY
MER CHEMISTRY 2.3

becomes more essential to know about the basic terminologies

Table 2.2
used before going in detail on the various aspects of polymer
chemistry. Polymer Structure Repeat unit

Iloly(ethylene) -H C-CH -CH2-CH2- -CH -CH -

2 2
Monomers 2 2

I'oly(styrene) -CH -CH-CH -CH-CH -CH -CH -CH-

Monomers are simple low molecular weight 2 2 2 2

substances that combine with each other to form high I I I I

Ph Ph Ph Ph
molecular weight substances called polymers. These
monomers may be solid or liquid or gas. Some examples for Poly(vinyl -CH -CH-CH -CH-CH -CH -CH -CH-
2 2 2 2
monomers are given in table 2.1 chloride) I I I I
Cl CI Cl Cl
Table 2.1
Polyacrylonitrile -CH2-CH-CH2-CH-CH2-CH -CH -CH-
2
Monomers Formula M.Pt/B.Pt Physical Polymer (OrIon) I I I I
(OC) state formed CN CN CN CN
,
Acrylonitrile CH2=CH.CN 78 liquid polyacrylo
nitrile gree of polymerisation
Ethylene CH2=CH2 -- gas polyethylene The number of repeating units in a polymer chain
known as degree of polymerisation and is denoted by the
Propylene CH3·CH=CH2 -- gas polypropylene rm DP and represented by the letter 'n',
CONH2
I MP
Acrylamide CH2 = CH 86 solid polyacryl- IOOO(CH2=CH2)(g) • -{-CH2-CH2-)-lOOO
amide
DP = 1000
Styrene CH2=CH 142-146 liquid polystyrene
I
MP
Ph
OOO(CH =CH.CN) • -{-CH2-CHCN-)-5000
2

Repeat units DP = 5000

Simple units that repeats in a polymer chain is called
In general,
repeat unir.-(Tabl~.2) .• MP
n (CH 2=CHX) • -(-CH 2-CHX-)-. n
 2.5
.YMER CHEMISTRY
2.4 ENGINEERING CHEMISTRY

Tacticity : The orientation of the repeat units or

DP = n= M onomeric molecules in space with respect to the main
m
in of the polymer is called tacticity of the polymer.
where 'M' is the average molecular weight of the polymer
and 'm' is the molecular weight of the monomer (or) repeat
CLASSIFICATION OF POLYMERS
unit.
Based on the following criteria, polymers are classified
Oligomers and Polymers: If the molecular weight of
nto different types as shown below.
the polymerised substance is in the order of 500 - 5000, they
are called oligomers. Polymerised substances whose molecular . Based on availability : Polymers are classified as natural
weight is in the range of 104 - 106, are known as polymers.
olymers and synthetic polymers.
Functionality : As the polymerisation involves the
merging of simple units (monomers) on either side, there must Natural polymers Synthetic polymers
be atleast two reactive sites in a monomer. The number of _..1..--1 _ 1
reactive sites of a monomer is termed as functionality of .l 1 ~ l
the molecule. Table 2.3 Inorganic Organic Inorganic
Organic
Table 2.3' polymers polymers polymers
polymers
Monomer Functionality Number of active
is due to sites \ Ex.m~les \
(Functionality) \
DNA, Clay Polyethylene Silicones
Ethylene double bond 2 Polypropylene
RNA
HOOC-{-CH2-~ COOH Carboxylic acid 2 Cellulose Polyvinyl chloride
Proteins polycarbonate
H2N-{-CH2-~ NH2 Amine 2
2. Based on the monomers
PhO - C - 0 - Ph
II Phenoxide 2 (a) Homopolymers : If the polymer chain contains the
0 same monomer as repeat units, such polymers are called
HO-{-CH2-CH2-~ OH alcohol 2 - mopolYffiers.
......... M-M-M-M-M-M-M ,
.
CH2=CH.CI double bond 2
(e.g.,) Polyethylene: -CH2 - CH2 - CH2 - C~ - CH2-
 2.7
,YMER CHEMISTRY
2.6 ENGINEERING CHEMISTRY\.
Uranched chain Branched chain copolymer
Polyacrylamide: -C~ - CH - C~ -CH - C~- homopolymer
I I
CON~ CON~ A-A-A-A-A-A- -A-B-A-B-A-B-
Polybutadine : -(-CH2-CH=CH-CH2-)-n I I I I
A A A B
(b) Copolymers: If the polymer chain molecule I I
I I
contains two different monomers, such polymers are called A A B A
copolymers. I I
I I
Alternating copolymers ross-linked polymers :
·········-M
-M -M -M -M -M _ . A
1 2 1 2 1 2

(e.g.,) Copolymer of stilbene and maleic anhydride I

-A - A - A - A - A - A -
(e.g.,) Polystyrene (co-divinylbenzene) I I
A A
I I

¢
-( -CH -CH-CH -CH-)- n
2 2
-A - A - A - A - A - A -
~h I I
A A
- CH-CH2- I I
-A-A-A-A-
Homochain polymers: If the main polymer chain contains
Polyvinyl chloride (co-acrylonitrile) repeat units having the same atoms, such polymers are called
-( -CH -CH-Cl-I - CH-)-
2 'L n
homochain polymers.
I I (e.g.,) Polyethylene (Carbon atoms in main chain).\
Cl CN

H H H H H
. Based on the structure of the repeat unit of the polymer I I
I I I
chain C- C- C- C- C-
I I I I I
(a) Linear homopolymer Linear copolymer H,
H H H H
-A-A-A-A-A- -A-B-A-B-A-B-
 2.9
2.8 ENGINEERING CHEMISTRY
LYMER CHEMISTRY

(e) Heterochain polymers: If the main polymer chain where R == CH3

, ,II
contains the repeat units having different atoms such polymers
are called heterochain polymers. H(
,
.. .
-,
R

(e.g.,) Nylon (Carbon and nitrogen atoms in main chain)

( HN-(-CH -) -NH - C - (CH) - C I Ii H H H H H H H

-C- 2 6 II 2 4 1I)n (i) Atactic polymers: If the similar substituents on the
o 0 repeat units of the polymer backbone are (randomly arranged
in space) in disorder, such polymers are called atacticpolymers.

(f) Graft copolymers: These are branched copolymers

in which the repeat units on the main chain and branched \
H",(
chain are different. ,,'

-A-A- A -A -A -A- H
H H
I I H H H
B B
I I (j) Syndiotactic polymers: If the similar substituents
B B on the repeat units of the polymer backbone are arranged in
I I an alternate fashions, such polymers are called syndiotactic
polymers. (e.g.,) Gutta Percha.
(g) Block copolymers: It is a linear copolymer where H
H R R (
a .£!.ock of one !YJle of repeat units is replaced by different
type of repeat unit.
<,

,
-A-A-A-A-B-B-B-B-
H H
(h) Isotactic polymers : If the similar substituents on H H
H
the repeat units of the polymer backbone are all on the same
side, such polymers are called isotactic polymers. on the
4. Based on the applications : Based
(e.g.,) polypropylene. applications, polymers are classified as follows:
(a) Plastics - Polyethylene, polystyrene
 2.11
LYMER CHEMISTRY
2.10 ENGINEERING CHEMISTRY
The monomers that undergo this type of polymerisation
(b) Fibres - Nylon, pterylene contain functional groups like -OH, -COOH, NH2, -COOR
(c) Elastomers - polystyrene, polybutadiene etc., If the reacting monomers contain more than two
functional groups, the polymers obtained are highly cross-
(]I] TYPES OF POLYMERISATION linked. Since the elimination reaction leading to chain
There are three types of polymerisation. They are rowth occurs in steps, condensation polymerisation is also
(a) Addition polymerisation called as step polymerisation.

(b) Condensation polymerisationlpolycondensation CO~

(c) Copolymerisation c.g., n I Q~l~O- C~ - CH2 - OH
(a) Addition polymerisation : Addition polymerisation
I .# Ethylene glycol

is common in monomers containing one or more double bonds. COOH

These polymerisation reactions are carried out by the action pterephthalic acid Condensation
of heat or light, under pressure and in the presence of a polymerisation
catalyst. Polyethylene, polypropylene, polystyrene are formed -nHp
by this type of polymerisation. Addition polymerisation is
also called as chain polymerisation. Here, the molecular
weight of the polymer formed is the integral multiple of 0- (CH2)2- 0 - C-\ )- C
molecular weight of the monomers. II II

~p
°
Polyester (pterylene)
° J n

n (CH2 =CH2) • ---'

, -CH 2-CH 2-)- n
Catalyst PE
Polyethylene
H2N-(-CH2-~ N~~CO -{-CH2 -h. COOH

(
n CH2 =CH
I
CN
~ Catalyst
-~-CH 2-CH 2-~- n
I
CN
Hexamethylene diamine Adipic acid

l-nHp
PAN
Polyacrylonitrile
HN -(-CH -) -NH-C-(CH )- C
(b) Condensation polymerisation : In this type of 2 6 II 2 4 II
polymerisation, reactions occur between two different
monomers and small molecules like H20, HCI, CH30H are nylon 6:6
° . 0
n
always eliminated.
 2.13
MER CHEMISTRY
2.12 ENGINEERING CHEMISTRY
(c) CopolymerisationlInterpolymerisation : This type
COMPARISON BETWEEpi ADDITION AND polymerisation reaction occurs between two different
CONDENSATION POLYMEItISATION nomers. Such polymers possess high molecular weight and
""able 2.4 are called copolymers. Such polymerisation reactions may
S.No. Addition Condensation cur by addition reaction.
Polymerisation Polymerisation
1. Addition polymerisation occur
between monomers containing
Here, the polymerisation
occur between molecules nlH2~t: J
+
nl~~cc J
double bonds. containing functional groups
Vinyl chloride
like -OH, -NH2 etc. Acry lonirtile
Copolymerisation
2. Addition reaction leads to the The polymers are formed by 1
polymer with the molecular condensation process
t-
CH2--C~--CH2~H
weight equal to the integral
multiple of the molecular
weight of the monomers.
involving elimination of small
molecules. Hence, molecular
weight of the polymer is less
than the integral multiple of
molecular weight of the
monomers.
1 CN

polyacrylonitrile
CI In
(co-vinylchloride)

3. Normally, homochain Heterochain polymers are

2. Styrene Butadiene Rubber (SBR)
polymers are formed. obtained.
n [CH2=CH-CH=CH2] + n [CH2=CH.Ph]
4. Chain growth occur at one Chain growth is due to
Butadiene Styrene
active centre. reaction at two active
centres. (75 parts) (25 parts)

1
5.

6.
Higher yields are obtained with
longer reaction time, but there
is no effect on the molecular
mass of the polymer.

High molecular weight

Longer reaction time results
in increase in the molecular
weight of the polymer.

Monomer reacts at a quick

l
cH-CH=CH-CH
222
Copolymerisation

-CH -CH

.
I
Ph
t n
polymers are formed rate but high molecular
immediately though weight polymers are formed Polybutadiene(Co-styrene)
monomer reacts at a at a steady rate.
(SBR)
steady rate.

7. Mostly thermoplastics are Mostly thermosetting plastics

formed. are formed.
 2.23
MER CHEMISTRY
2.22 ENGINEERING CHEMISTRY

NGINEERING PLASTICS
Plastics are classified into thermoplastics and
Plastic materials that are used for engineering
thermosetting plastics based on the difference in the thermal
piications are referred to as engineering plastics. Certain
behaviour. They are classified into commodity plastics and
Illstics possess special properties such as strength and
engineering plastics, based on the application.
ughness of metals, rigidity of wood, transparency of glass,

Commodity Plastics at resistance of ceramics etc.

The commodity plastics possess low to moderate Hence such plastic materials can replace the conventional
strength. These are commercial plastic materials used for the ngineering materials such as metals, wood, glass, ceramics
manufacture of general purpose items. These plastics possess tc. In some cases, these plastics in conjunction with
the following properties
onventional engineering materials offer many advantages.
(a) Moderate Mechanical strength
(b) Poor dimensional stability
lcquirements of engineering plastics:
(c) Low abrasion resistance
The 'plastic materials to be used in engineering
(d) Very poor thermal stability Ipplications should possess some of the following properties
(e) Mostly water resistant
(f) Corrosion resistant l. Good dimensional stability
(g) Poor conductors of electricity High abrasion resistance
2.
Examples for commodity plastics 3. High rigidity
Table 2.5 Toughness
4.
Polymers Uses High load bearing strength
5.
Low density polyethylene Films, Table cloth 6. High thermal stability

High density polyethylene Toys, pipes, drums 7. High mechanical strength

8. High corrosion resistance

Polypropylene Laboratory articles
9. High chemical resistance
Polyvinyl chloride Rain coats, electric cables
10. Fair degree of flexibility
Polystyrene Radio and television parts
 2.24 ENGINEERING CHEMISTRY ,YMERCHEMISTRY 2.25

11. High dielectric cosntants FERENCES BETWEEN THERMOPLASTIC

"SINS AND THERMOSETITNG RESINS
12. Good tensile strength
] 3. Light weight Table 2.6
-.....:,..
14. Durability Thermoplastic Thermosetting plastic
~.No
resins resins
The preparation, properties and application of some of
the engineering plastics are discussed later in this unit. I. They soften on heating Action of heat do not
and harden on cooling. effect any physical

GIJ PLASTICS
THERMOPLASTICS AND THERMOSETTING
change.

2. Forces acting between Adjacent polymer chains

the polymer chains are are linked by strong
Based on the thermal behaviour, plastics are classified
weak Van der waals covalent bonds.
into thermoplastics and thermosetting plastics.
forces.

Thermoplastics : These are polymeric substances 3. They are formed by Condensation

that soften on heating and becomes hard (or) rigid When
~,'" -' • -. . •••
-. '--- ••.
,... • .• I addition polymerisation polymerisation results in
cooled. The physical transformation OCcur in a reversible reaction. thermosetting plastic
manner but there is no change in the chemical structure. resins.
Polymers formed by addition polymerisation are in general, A. They can be reused and They cannot be reused.
thermoplastic in nature.
remoulded.

Thermosetting plastics : These are cross linked 5. They are soft and weak They are hard and strong
polymers that are hard, rigid and brittle. They withstand but less brittle. but more brittle.
high temperature but do not soften on heating. At very
6. They are soluble in They do not dissolve in
high temperature, chaning occurs. During the preparation of organic solvents. organic solvents.
such resins, by heating, cross linking by strong co-valent bonds
OCcur which makes them hard. 7. Thermoplastics are Thermosetting plastics
generally low molecular have high molecular
weight polymers. weights.
,
 2.31

2.30 ENGINEERING CHEMISlli R CHEMISTRY

_----1l"
ou
(5) Table cloth, curtains, rain coats II 1 cii,5H ~
OH
H<'lH2C~~H2\.A.!
OH OH

(6) Insulation tape for electrical covering \11 +I#, +V +U

~
~BAKELITE
OH OH OH rnl
It is a thermosetting
condensation
plastic material
reaction of phenol with formaldehyde.
formed h,
The
'ij"lYH2'ijH"6
reaction takes place in the presence of acidic or alkaliru Novolac
catalyst as shown below.
Novolac is soluble in alkali and it is fusible. It has low
Step (i) : Hydroxy methylation of phenol with HCHO
molecular weight.

6
OH OH
tep (iii) F?rmation of Resole
CH20II
+ HCHO -
o-Hydroxymethyl
&
I ~
phenol
In the presence of alkaline catalyst and with excess of
Illlll1aldehyde (less phenol), the following reactions occur.

OH OH
OH OH OH OH
H'OCH20-CH?D -
HCHO
Q'CH 0H 2 HCHO
-
HOH2C\¢1CH?OH
~
I
I
-
II~H2~OH2C~

U + U
""'"

1 """ \
""'"

"""

~ Resole

CHpH CI-I20H
Step (iv) : Formation of Bakelite
2,"-di(hydroxymethyl) phenol 2,4,6-tri (hydroxymethyl) phenol
The condensation products Novolac and resole when
Step (ii) : Formation of linear polymer (Novolac) treated with hexamethyle tetrarnine «CH2)6N4)' highly cross
linked polymer, bakelite is formed. Hexarnethylene tetramine
2-Hydroxymethylphenol in presence of acidic catalysts
provides the required formaldehyde units .
reacts with excess phenol and results in the formation of linear
polymer called Novolac.

..
 2.32
ENGiNEERING CHEMISTRY

OH 011 01-/

H!UCH?V
I
~ -
I
...", -
I
...",

~ ..9- ..9- ..9-

6'"
OH
c.
Ar~ :/'CII(y\
011
~2

011

Bakelite
Properties
I. It is a rigid, hard and infusible polymer.
2. It is resistant to water, acids, organic solvents but
easily attacked by alkalis.
3. It is an insulator.
Applications

1. It is used in the manufacture of switches, plugs

and switch boards.

2. It is used for making molded articles like telephone

parts, radio and television parts.
3. It is used as adhesive in plywood.
4. As ion exchange resin in softening of water.
S. Eor impregnating fabrics, wood and paper.

POXY RESINS.

Preparation ,
It is prepared fro~ epiclllorohydrin and Bisphenol as
shown below:
 l YMER CHEMISTRY 2.35

~.llIEFFECT OF POLYMER STRUCTURE ON

PROPERTIES

Chemical structure of a polymer greately influence their

physical properties. The important physical properties are
Iiiscussed below .

. Plastic deformation : Thermoplastic resins possess

.1 linear structure and the polymeric chains are held by weakVan
dcr waals forces. These forces get disrupted at high pressures
and much more disrupted at high teI?perature. Hence, one
layer of polymer chain slides over the other. This explains the
deformation in shape at high temperature and at high pressures.

In case of thermosetting plastic resins, the high degree

of cross links by strong covalent bonds will not allow any
deformation in shape at high temperature or at high pressure.

(.;2. Strength : The strength of the polymer depends on

the extent and type of intermolecular forces between the
polymer chains. In branched and straight chain polymers of
greater chain length (more than 200 atoms in a chain) and
higher molecular weight, Vander waals forces of attraction
between the polymer chains is much greater and hence the
polymer is tough and thermally more stable .. (e.g.,) HDPE.
 2.36
ENGINEERING CHEMISTRY l YMER CHEMISTRY 2.37

Presence of polar functional groups like hydroxyl, carboxyl,

3. Slipping power: Polymer molecules that are linear
flourine etc., increases the intennolecular forces and contribute with uniform and simple structure, one chain can easily slide
more to the polymer strength, (e.g.,) PVe.
liver the other without restriction (e.g.,) PE. But if the polymer
chain is branched or if it contains substituents, then the
restriction for movement becomes more and hence the slipping
power decreases (e.g., PVC).
~
. Crystallinity: Crystallinity is a measure of orderliness
(If the polymer chains with respect to each other. A complete

random arrangement of the polymer chains results in

HDPE amorphous state. A regular and orderly arrangement of the
polymer chains result in a crystalline polymer.

Polymers with higher chain length and more substitution

along the polymer chain lack symmetry and hence do not
@ @ @ @ crystallize easily. This results in amorphous state of the
polymer. (e.g.,) Polystyrene (PS), Polyvinyl acetate (PVA),
Polymethyl methacrylate (PMMA). (Fig. 2.2)
~. Polyvinyl chloride (PVC)

In a cross linked polymer,

the polymer chain are linked by ~
strong covalent foces, which 'c
<IS
\)Cfj'l~\

~~~h
III
makes them much more stronger ~
than the linear and branched
polymers.
degree of
In general, as the
polymerisation
!
~o
l
W~'0
.~
increases, the tensile strength of .......-- J (q
(el IbI
the polymer also increases. Tensile Strength
(Fig. 2.1)
I Schematic representation of: (a) amorphous polymer, (b) crystalline polym.r
Fig. 2.1
embedded in an amorphous matrix, and (c) oriented crystal!ine polymer.
,

Fig. 2.2
 2.39
~MER CHEMISTRY
2.38 ENGINEERING CHEMISTRY
vement of polymer chains just starts from its original
5. Chemical resistance : Addition polymers that are
linear or branched with non-polar and more aliphatic nature sition.
swell in aliphatic non-polar solvents. (e.g.,) Swelling of Melting point of the polymer: It is the temperature
polypropylene is more in petrol or carbon tetrachloride. yond glass transition temperature (Tg) that causes the phase
Polymers of aromatic nature are more soluble in aromatic banges glassy state - flexible mass - liquid state. The melting
solvents such as benzene or toluene. int is sharp for a crystalline polymer.

But amorphous polymers do not have a sharp melting

But these polymers are resistant to dissolution in polar
into But they soften on heating and at low temperatures
solvents. Polymers containing polar groups such as -OH,
ey are glassy and brittle. When heated beyond T , amorphous
-COOH, -NH2 etc., dissolve more readily in polar solvents lymers become more flexible mass, and then ~y. Further
such as water, alcohol (e.g.,) polyvinyl alcohol -H20. But heating to high temperature results in the liquid state.
these polymers are more resistant to dissolution in non-polar
T of a linear polymer is lower than T of partially cross-
solvents.
linked ~olymer. The value of T g depends Jpon the
Highly cross linked thermosetting polymers are more
(i) chain length, (ii) degree of cross-linking, (iii) the
resistant to most of the organic solvents. In general, the extent of restriction for internal rotation around the polymer
swelling power (or) solubility of the polymer decreases with
chain.
increase in molecular weight. The rate of dissolution of ,
crystalline polymers is slower than that of polymers with low Glass ••.. Crystalline and
molecular weight. glass

"
flexible
6. Effect of heat on polymers : The polymers that R\1bber Tg (OC) A:.

soften on heating are thermoplastics. These molecules gain --------- ---------

T-
thermal energy and the sliding of polymer chain one over the
other occurs. When these are cooled to very low temperature, (OC)I Gum o
the movement of polymer chains is arrested and the polymer liquid
liquid
mass appears glassy and it is brittle.
Crystalline polymers
Amorphous polymer
Glass transition temperature : The temperature at
Fig. 2.3
which the polymer molecules gain enough energy and a