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General Introduction

1.1 Introduction
A polymer may be defined as a substance built up of a number of repeating
chemical units held together by chemical bonds. A high polymer is one in which
the number of repeating units is in excess of about 1000. This number is termed
as “Degree of Polymerisation (DP). The molecular weight of a polymer is
often given by the product of the molecular weight of the repeating units and DP.
The compound or compounds, used in the preparation of polymer are called
monomers. The repeating units constituting the polymer molecule are called
constitutional repeat units (or CRU). Fig. 1.1 illustrates the monomer, DP and
CRU for polyvinyl chloride.

(i) Monomer : Vinyl chloride

ape
1

l (ii) DP: 1000

o
i
C
CH
Cl
PVC

(iii) Molecular weight of polymer

= Mol. Wt. of monomer x DP
= 62.5 x 1000
= 62,500

(iv) CRU CH) — CH

Cl

Fig. 1.1 The monomer, DP, molecular weight and CRU in polyviny! chloride (PVC)

It is important to note here that the term polymer was first used by Berzelius
in 1827, but the concept of polymer as molecule with high molecular weight (at
2 Principles of Polymer Science

least few ten thousands) was introduced by the German Scientis Hermann
Staudinger almost a century later (in 1920) which was at that time severely
criticised. A macromolecule is the term interchangeably used for polymers,
more often of biological origin. For example insulin, a protein-like hormone, is
made up of several different amino acids (51 in total) and can be called as a
macromolecule but not strictly as a high polymer. Note all the substances can be
polymerised. It is necessary that a chemical substance can act as monomer only
if it has at least bi-functionality (which could be due to one double bond or two
reactive functional groups).
As stated before, the bi-functionality may result due to the presence of at
least a double bond (like in olefins) or two reactive functional groups (two -OH
groups in ethylene glycol).

H,C=CH, -(CH,— CH2};

Ethylene Polyethylene

HO—CH, —CH,— OH (CH) CH, —0>-

Ethylene glycol Polyethylene glycol

Let us consider following examples to show that bi-functionality in a monomer

is a must for the growth of a polymer chain through the reaction of functional
groups successively. For two compounds each possessing only one functional
group (as in the case of acetic acid and ethy! alcohol), the reaction is complete
in one step leading to the formation of ethyl acetate.
O
ene 3
CH wheat a, HOCH, —CH,
Acetic acid | Ethy! alcohol

O
I
CH C—O
CH s-CH,
Ethyl acetate

For a reaction between two compounds one possessing a monofunctional

group such as a carboxylic group in acetic acid and the other with bifunctional
groups of two hydroxyl groups in ethylene glycol, it can be easily seen that the
reaction completes in two steps leading to a monoester (I) in the first step. In the
second step the pre-formed monoester reacts further with one molecule of acetic
acid to yield a diester (II). Since the diester do not have any more reactive
functional groups on its either sides, no further reactions take place. Thus it can
be seen that when diester or any other intermediate which do not have any
reactive functional groups, are formed no polymer chains are resulted.

| i
HO—CH,—CH,+OH + HO—C—CH,
Ethylene glycol | Acetic acid

|
HO—CH,—CH,—O—C—CH,
Monoester
(1]
 General Introduction 3

[I] combines with another molecule of CH,;COOH in the second step to form a
diester [II];
IInd step O
Dees ]

10>
Ci 6 0in4NO.CH—CH,-0—C—CH,

I |
CH3;—C—O—CH,—CH,—O—C—-CH,
Diester
(1)
Now if we consider a reaction between two compounds each containing two
reactive functional groups (e.g. ethylene glycol and malonic acid), it can be
inferred that the addition of each of the monomer to another continues till the
concentration of one of the species is depleted. Then one can have high molecular
weight polymers formed from these bifunctional monomers.
HO=Ch=Ch—0n"+-H0OC=CH.—COOH

Ig
HO—CH,—CH,—-O—C—CH,—-COOH
Monoester

Monoester can combine with either the glycol or the malonic acid at the
corresponding functional group end to facilitate further growth of the chain;

] l
HOj;-C—CH—C=OHu+? HO—CH,=—CH,-0H
+

i
HOs-CH.
CH) —0 CCH GOoH
Monoester

O
| I
Hot Gu, ¢ 9 occ, C0 _cH,_-cH, on
Diester

Thus if n moles of a bifunctional species such as malonic acid is reacted with

the same number of moles of ethylene glycol which has two reactive hydroxyl
groups on both the ends, the esterification reaction occurs step wise forming
mono, di-, tri-, tetra-, multi- and polyesters (see the following scheme).
4 Principles of Polymer Science

Qt 71 ND
i i
nHO—C—CH,—C—OH + nHO—CH,—CH,—OH

O
I
HO--CH—CH)—0+6=Ciy==—0)41
Polyester

Thus, the reaction between two bifunctional molecules leads to a linear high
polymer. Further, if we add some trifunctional group, it may form either branched
polymeric chain or a three dimensional network structure.
The reactions between different molecules is schematically shown in Fig. 1.2

Monofunctional Molecules:
—e +x ——_r> —ox

Mono and Bifunctional Molecules:

—e +x——x ——, —e x—KX

|
—e x xX e—

Bifunctional Molecules: Small Molecule

x baer ee
| Nf poh Rs oe X——X @—e® X——-X @—@ X——-X
x x Xx——xX
Nf Linear Polymer Molecule
X——x 5 ign

Bifunctional Molecules in presence of some Trifunctional Molecules:

. ~ x——X e—o X———X
ee
ee

ionx

x Tft x ay
oes
|

Cross linked or Polymeric Network

Fig. 1.2 Reactions between molecules with different functionality

1.2 Classification of Polymers

There are several ways to classify polymers. The classification is based on
 General Introduction 5

several considerations. The source of polymers i.e. natural or synthetic, the type
of polymerisation process used in the synthesis, nature and type of chain and
solid state behavour of polymer chains etc. The different classification schemes
can be outlined as shown in Fig. 1.3.

Natural and synthetic polymers

P ‘
O Addition and condensation polymers
L
¥ Homochain and heterochain polymers

E
R Monodispersed and polydispersed polymers

Organic and inorganic polymers

c Homopolymers and copolymers

Ig
A
S Linear, Branched and cross-linked polymers
S
I
F Charged and uncharged polymers
I
ie
A Thermoplasts and thermosetts
all
I :
O Fibers, plastics and elastomers
N
Crystalline and amorphous polymers

Isotactic, syndiotactic and atactic polymers

Fig. 1.3. Classification of polymers

Most linear polymers take on new shapes by the application of heat and
pressure. They are thus called ‘thermoplastics’ whereas the cross-linked polymers
cannot be made to flow or melt irreversibly and are said to be ‘thermosetting’
resins. The differences between these two types are listed in Table 1 (a). A
polymer may contain monomers of identical or different chemical structure.
Polymers made up of only one type of monomeric units are called ‘homopolymers’
whereas those polymeric compounds which are built up of two different types of
monomer units in their chain are called ‘copolymers’ (or mixed polymers).
Polymers with three different types of monomeric units are some times called
‘terpolymers’. The advantage of such polymeric structures is that a single polymer
molecule can have the properties of both the entities, which cna be selected
suiting to the end use of application. Such possibility hardly exists in simple
molecules.
Copolymers are further classified as alternating copolymers or statistically
regular (where both different repeating monomeric units are joined side by side)
and random copolymers or statistically irregular (where there is no regularity in
6 Principles of Polymer Science

Table 1(a) Comparison between thermoplastics and thermosetts

Thermoplastics Thermosetts

They are often formed by addition They are often formed by condensation
polymerisation leading to long polymerisation and three dimensional
linear chain polymers with no network structures are formed
cross-links
They soften on heating readily, They do not soften on heating, On
because secondary forces between prolonged heating, however charring
the individual chains can break of polymers is caused
easily by heat or pressure
en They can be reshaped and reused They can not be reshaped and reused
They are usually soft, weak and They are usually hard, strong and more
less brittle brittle
i These can be reclaimed from wastes They can not be reclaimed from wastes
They are usually soluble in suitable Due to strong bonds and intra- and
solvents interchain cross-links, they are
insoluble in almost all organic solvents

the joining of units of two different monomers). Copolymers can also be of

block or graft types. In Fig. 1.4 are schematically shown structures of different
homo-, co- and ter-polymers made using the monomers A, B and C.

(1) Homopolymers: www AAAAAAAAAAAAA

Awww

(2) Copolymers:

(a) Alternating: Www ABABABABABABABwwv

(b) Random: ww» ABBABAAAABAABAwww

(c) Block (two block): wwww+§ AAA AAAABBBBBBBwww

(three block): Www A AAAABBBBBAAAAWw

www BBBBBA AAAABBBBwwww
(d) Graft: MARA AAAAR BAAR AAI

(3) Terpolymers:) wwwABAACBAACCAABwww

Fig. 1.4 Molecular architecture of homo-, co- and terplymers

Polymers can be classified as linear, branched or cross-linked polymers. High

density polyethylene (HDPE) is a linear polymer, while low density polyethylene
(LDPE) is a branched polymer. Natural rubber has two configurational forms.
The cis form has less density and is available as latex. The other form is the trans
 General Introduction 7

form and is brittle and hard (gutta percha). Further the natural rubber on
vulcanisation (or mastication with sulphur) develops crosslinking and becomes
processable. The various topologies of the polymer chains are schematically
presented in Fig. 1.5.

Lineat polymers) =< > 7

Branched polymers:

Cross linked polymers:

(Network) Sen

Fig. 1.5 Schematic representation of linear, branched and cross-linked polymers

According to the structure of their main chain, all polymers can be broadly
classified as homochain and heterochain polymers. In case of homochain polymers
the main chain is made up of linkages between the atoms of same element e.g.
carbon in organic polymers.

In heterochain polymers, the main chain consists of linkages between different

atoms e.g. between carbon and oxygen in polyester, polyethers, carbon, nitrogen

toftot
and oxygen in polyurethanes etc.

Polymers are also classified as organic, elementoorganic and inorganic polymers.

Organic polymers have chains consisting of C—C linkages and have apart from
carbon atoms, hydrogen, oxygen, nitrogen, sulfur and halogen atoms in the side
chains. Elementoorganic (or hetero organic) polymers include (i) macromolecules
whose chains are composed of carbon as well as heteroatoms (except N, S, O
and halogen atoms) and (ii) inorganic chains in which side groups contain carbon
atoms directly linked to chain. Inorganic polymers are polymers containing no
carbon atoms but have Si—Si, Si—O, N—PX, P—O and B—O linkage e.g.
polysilanes, polysiloxanes, polyphosphazenes, polyphosphoric acid or
polyphosphates and poyboron oxides. Inorganic polymers have been studied to
a little extent so far and it is difficult to provide a classification. However inorganic
polymers posses superior thermal, electrical and mechanical properties over
the organic polymers. Silicones, polyphosphazenes and several organometallic
and coordination polymers are from this class and worth mentioning (these are
8 Principles of Polymer Science

described in detail in chapter 7). Soe common inorganic polymers are shown in
Fig. 1.6.

Polysilanes:
fe dele gel ie!
svete Si—Si—Si—Si ann
HoH OH
Polyphosphoric acid:

Polysilicic acid:
OH ne ‘i io
3h. aa cf am a Mee AMAMAMARAAM
OH OH OH OH
Polymeric sulfur:
ways SSS -—S-S-_S_ www
Polyphosphazene:
a « Cl a
cans gutaine cehia Nae N—P www

Cl Cl GI Cl
Polyvinyl crown ether:
~as
CH —CH. 5Wye

Ve an
‘a .SS a,”
N‘ ,‘
‘N \, ‘\
‘,
, ‘\ ‘\
} jo)

Fig. 1.6 Some common inorganic polymers

Polymers in which the side branches are present in every unit, being joined by
different chemical groups with the main polymer chain are known as comb-like
polymers. Branched polymers which resemble a star by their structure are known
as star like polymers. Collinear double chain polymers are known as ladder
polymers. Model structures for various branched polymers are shown in Fig. 1.7.
Polymers can also be classified as (1) natural or (ii) synthetic. The common
natural polymers include polysaccharides (starch, cellulose, gums etc), proteins
(gelatin, albumin, enzymes, insulin), polyisoprenes (natural rubber, gutta percha)
and nucleic acids (RNA and DNA). Natural polymers are sometimes also called
‘Biopolymers’ or “Biological macromolecules’.
Polymers can also be classified further as fibers, plastics, resins and rubbers
 General Introduction 9

So
Suatg Random comb Regular comb

LUM THIET
Fig. 1.7
Ladder Semiladder
Possible model structures for branched and cross-linked polymers

based on the nature and extent of secondary valence forces and mobility among
the constitutional repeat units. Important examples belonging to each class are
shown in Table 1(b).

Table 1(b) Some important polymeric materials useful as plastics, fibers, rubbers
and resins

Form Type Polymeric material

Fibers Natural Cotton, wool, silk and asbestos

Semsynthetic Viscose rayon, acetate rayon and cuprammonium
(Cellulosic) rayon
Synthetic Polyamides, polyesters, acrylics, polyurethanes,
polyolefins, polypropylene, polyvinyl! chloride,
polyvinyl! alcohol
Plastics Cellulosic plastics Celluloid, cellophane
Vinyl plastic Polyolefins-(polyethylene, polypropylene,
polytetrafloroethylene (teflon)), polystyrene,
polyvinyl chloride, polyvinyl acetate,
polyvinylpyrrolidone,
Polyacryloids polyacrylic acid and polymethylmethacrylate
Rubber Natural polyisoprene (cis-1, 4) polydiene (e.g.
Synthetic polybutadiene, polychloroprene and polyisoprene),
butadiene copolymers (e.g. NBR, SBR or
Buna N and Buna S), butyl rubber, polyurethanes,
polysulfides and polsysiloxanes (silicone rubber)
Resins Water Solube Modified starches, cellulose derivatives, polyvinyl!
alcohol, polyvinyl pyrrolidone, polyacrylic acid
and polyacrylamide
Water Insoluble Phenol plasts and amino plasts, polyurethane
resins, silicone resins, epoxy resins and unsaturated
polyesters
10 Principles of Polymer Science

Plastics, fibers and elastomers possess different physical properties. While

fibers are crystalline materials, elastomers are amorphous. Plastics lie between
these two extreme cases in physical properties viz. modulus and elongation as
shown in the Table l(c).

Table 1(c) Physical characteristics of polymers

Polymers Modulus, dyne cem~? Elongation, %

Elastomers 105-10" 1000

Plastics 10° 10" 100 — 200
Fibers 10° — 70" 10 — 30

Polymers may be charged or uncharged. Charged polymers have some free

functional groups e.g. polyacrylic acid (anionic polymer) or polyethylimine
(cationic polymer). Charged (or ionic) polymers that are soluble in water are
called as “polyelectrolytes”. Water insoluble charged polymers are often called
“jonomers”’.
Polymers may also be classified as amorphous or crystalline depending
upon their morphological behaviour. These two types of polymers behave differently
as crystallinity influences the properties such as hardness, stiffness and elasticity,
thus making them useful as plastic, rubber, fiber or resin. LDPE is less crystalline
and while HDPE is highly crystalline polymer. However it is important to note
that solid polymers when crystallised hardly attain hundred percent crystallinity.
Thus solid state of polymers is often characterised by both amorphous and
crystalline domains. The two polyethylenes have different properties as shown
in Table 1(d).

Table 1(d) Properties of LDPE and HDPE —- a comparison

LDPE HDPE

Branched (% crystallinity < 50) Linear (% crystallinity > 90)

Density, 0.92 g cm™? Density, 0.96 g cm?
Softening point, 360 K Softening point, 400 K
Tensile strength, 85-136 atm Tensile strength, 205 — 315 atm

Linear low density polyethylene (LLDPE) is now manufactured and has less
branching. The linearity provides the polymer strength and branching gives
toughness.

1.3. Nomenclature of Polymers

Polymers are prepared by addition polymerisation of an unsaturated monomer or
by step polymerisation of monomer (or monomer pair) containing at least two
functional groups. The nomenclature of addition polymers is relatively simple.
Condensation polymers, for example, terylene and nylons are named according
to the repeat unit.
Addition polymers are usually named by prefixing poly- before the monomer
 General Introduction 11

from which the polymer is derived. For example polyvinyl chloride and
polyethylene are synthesised from vinyl chloride and ethylene monomers,
respectively.
Copolymers are named by inserting -co- (or -alt-, -rand-, -block-, or -graft-
if the position of the two monomers is known) as prefix. For example; poly
(styrne-co-butadiene) is a copolymer of styrene and butadiene and poly (styrene-
block-butadiene) is a diblock copolymer of styrene and butadiene. It is also a
common practice to designate a diblock copolymer as styrenebutadiene copolymer
and a triblock copolymer as styrne-butadiene-styrene block copolymer. An AB
block copolymer is also designate as poly (A-b-B) and an ABA copolymer as
poly (A-b-B-b-A). The block sequence arrangement of a diblock copolymer is
also represented by a long dash such as A—block—B and the corresponding
copolymer as poly A—block—poly B.
A wide diversity exists in naming polymers viz. based on source, structure,
industrial names, trivial names and even IUPAC names. The nomenclature of
few polymers has been illustrated in Table 1(e). However no single nomenclature
is universally adopted.
IUPAC names of some other common polymers are polystyrene (poly-(1-
phenylethene)), polyphenylene oxide (poly(oxyl, 4 phenylene)) and polyvinyl
chloride (poly (1-chloroethene)). Similarly IUPAC names for various monomers
are; adipic acid (1, 6 hexandioic acid), acrylonitrile (propennitrile), bisphenol A
(2, 2, bis-4-hydroxyphenylpropane), butadiene (1, 3-butadiene), caprolactam (2-
oxohexamethyleneimine), chloroprene (2-chloro-1, 3-butadiene), divinyl-benzene
(1, 4-diethenylbenzene), ethylene glycol (1, 2,-ethane diol), ethylene oxide (1, 2
epoxyethane), hexamethylene diamine (1, 6-hexanediamine), isoprene (2-methy]
1, 3-butadiene), melamine (2, 4, 6-triamino-s-triazine), methacrylic acid (2-
methylpropenoic acid), styrene (ethenyl benzene), terphthalic acid (benzene-|,
4-dicarboxylic acid) and vinyl chloride (chloroethene). Also, these IUPAC names
given in the parenthesis are seldom used in the polymer literature.

1.4 Isomerism in Polymer Chains

Various types of isomerisms are possible in case of polymers. These can be
grouped as constitutional, orientational, geometrical or stereoisomerism as shown
in Fig. 1.8.
A good example of constitutional isomerism is that of the monomer with the
CRU as C>H,O. Three different polymers viz. polyethylene oxide, polyvinyl
alcohol and polyacetaldehyde are possible, each one has quite different property.
It is not always that a polymer chain possesses regularity; any polymer which
lacks such an ordered arrangement, is called irregular. Polydienes, for example
1, 2- and 1, 4-polybutadienes show chain irregularity. In case of polyisoprenes
(1, 2-; 3, 4-and 1, 4- isomers) are possible. Chain irregularity may be of different
kinds e.g. polymerisation of vinyl polymers gives rise to ‘head to tail’ (major) as
well as ‘head to head’ or ‘tail to tail’ (minor) products as shown in the Fig. 1.8.
The stereo isomerism in polymer chains leads to tacticity (spatial order of
arrangement). Based on tacticity, the macromolecular substances are divided
into three categories as shown in Fig. 1.9.