Polymer & Its Classification

Dr. Md. Nurnobi Rashed

PhD in ICAT (HU, Japan), Postdoc. (AIST, Japan)

Lecturer
Department of Chemistry, BUET.

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 Polymer

• The word polymer derived from two Greek words “poly” and “meros”.
Poly means many and meros means parts or units.
• So a polymer may be defined as the molecule in which many units of a
single or two different molecules are united together by covalent bond.

…….(CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2)……..

Criteria of a polymer
❑ High molecular weight
❑ Composed of many monomer units
n(CH2=CH2) (CH2-CH2)n, n= No of repeating units or monomer
❑ The monomer units are joined together by covalent bond.

The starting molecule from which the polymer molecule is formed is called monomer

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 Is (NaCl)n crystal and (H2O)n ice is polymer?
United together by
(NaCl)n ionic bond
United together by Macromolecule
(H2O)n Hydrogen bonding
Polymer

What are the differences between macromolecules (Carotene,

vitamin C etc.) and polymer?

Composed by same
Polymer
repeating unit (monomers)
Composed by any repeating
Macromolecules
unit
Polymers are macromolecules, but not all macromolecules are polymers. The main difference
between a polymer and a macromolecule is that polymers contain repeating units that represent
monomers whereas not all macromolecules have a monomer in their structure.

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Classification of Polymers: There are various ways by which polymers may be
classified.

1) With respect to the degree of polymerization

(i) High polymers: The average molecular weight of high polymers lies
within 104 to 106. In this high polymer the degree of polymerization
(no. of repeating units) is more than 100 units.

(ii) low polymers: Low polymers are also known as oligomers. In this low
polymer the degree of polymerization (no. of repeating units) is less
than 100 units. (Oligomers)
✓ The length of the polymer chain is specified by the number of' repeat units in the
chain. This is called the degree of polymerization (DP).
✓ The molecular weight of the polymer is the product of the molecular weight
of' the repeat unit and the DP. Using poly(viny1 chloride) as an example, a
polymer of DP 1000 has a molecular weight of 63 x 1000 = 63,000.

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2) Depending upon the sources of polymer it may be classified as

a) Natural polymers: The natural rubber is cis-polyisoprene (-CH2-CH= C(CH3)-

CH2-)n.All Trans polymers are made in laboratory......

b) Synthetic polymers: Synthetic polymers are man made polymers. These are
synthesized in the laboratory. The examples of synthetic polymers are
polyethylene (polythene), nylon, polyvinyl chloride, teryline, styrene, butadiene
rubber etc.

Synthetic polymers are mainly divided into two types

i) Linear polymer:
Linear polymers are the polymers, in which the repeating units are linked in
a straight chain.

✓ The chain flexibility always appears. This is due to internal rotation

around the single bond. As a result coil of chain invariably exhibits in
linear polymers.
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 ii) Branched polymer:

Branched polymer may be defined, as the polymer in which some of the

monomer units are attached to the main linear chain as side chain.

✓ The length of the side chain may be different

✓ The branching may be random
✓ It may occur at regular intervals with equal length of branches
✓ Sometimes the branches may join to each other and in some cases
may join to the adjacent chain also

As a result, different types of branching providing different

mechanical properties appears in the branched chain polymers.

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 The various types of branched polymers are shown

Various types of structural polymers: (a) linear, (b) branched, (c) comb
type, (d) ladder type, (e) network type.

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3) Organic polymer and inorganic polymer
➢ Organic polymer may be defined as the polymer in which the backbone
chain is essentially made up of carbon atoms. The other valences of
carbon atoms are satisfied with atoms of hydrogen, oxygen, nitrogen,
sulfur, chlorine etc.

✓ Almost all natural polymers are organic polymers.

✓ In comparison to the huge number of organic polymers the number of
inorganic polymers are very limited.

➢ Inorganic polymer may be defined as the polymer in which the backbone of the
chain is made up of atoms other than carbon atom. Examples of inorganic polymer
are Glass, Silicon rubber, Titoxanes, Poly phosphoric acid, Poly phosphates, Poly
arsenates etc.

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 Mosarrof korim is a silicon rubber

Some structures of Inorganic Polymers

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 4) Depending upon the mechanical properties

(i) Thermoplastic polymer

(ii) Thermoset Polymer

i) Thermoplastic polymer:

• Thermoplastic polymers are the polymers, which become soft on heating and can
be given any desired shape.

• These polymers are able to retain that given shape on cooling.

• However, on further heating they become soft again with deformation of given
shape.

• polyethylene, PVC, polystyrene, nylon etc.

Thus the softening on heating and stiffen on cooling

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 ii)Thermosetting Polymer:
o Thermosetting polymers may be defined as the polymers, which become soft
on heating and can be given any desired shape and the shape is retained on
cooling. (Same as thermoplastic)

o But during heating this type of polymers undergo some chemical changes in
their structure and convert themselves into infusible and insoluble masses. As a
result, on further heating they never be soft again.

o At extremely high temperature these polymers decompose but do not soft.

Thus thermosetting polymer cannot be recycled.

o Melamine, epoxy resins etc

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 Bakelite is an example of thermosetting polymer. The polymer of this
type undergoes a permanent change upon melting and there after sets to a
solid mass on cooling which cannot be remoulded.

This may be attributed to excessive cross-linking between the chains

forming a three dimensional network structure on heating.

Thermosetting polymer Thermoplastic polymer

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 Key Differences between Thermoplastics and Thermosetting

1) Thermoplastics which can be easily melted and molded into a new article while
thermosetting plastics which when molded once, cannot be easily remolded by heating.
2) Thermoplastics can be recycled or reformed while thermosetting plastics cannot be
recycled or reformed. +++++
3) Thermoplastic can be synthesized by the process called addition polymerization while
thermosetting plastics are synthesized by condensation polymerization.
4) Thermoplastics have a low melting point while thermosetting plastics have a high melting
point.
5) Thermoplastics have low tensile strength while thermosetting plastics have high tensile
strength.
6) Thermoplastics have secondary bonds between molecular chains while thermosetting
plastics have primary bonds between molecular chains and held together by strong cross-
links.
7) Thermoplastics are long chain linear polymers but hermosetting plastics have three
dimentional cross-linked network structure joined by strong covalent bond.
8) Thermoplastics can dissolve in some organic solvents where thermosetting plasatics are
insoluble in almost all organic solvents because of the presence of cross linking and strong
covalent bond
9) Thermoplastics are subjected to disruption by heat while thermosetting plastics can
withstand high temperature without losing its rigidity.

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 ek basay dui baccha chilo jar ekjon
chilo shetango , tar chul chilo streight
(thermoplastic),se lomba ar chikon
chilo, arekjon chilo nigro, tar chul
chilo jot pakano, mane bola jay
condensed chul (thermosetting), se
primary school e porto. se chilo khato
ar onek mota. to ekdin tader basay
agun laglo. tader basha chilo 10 tala
building er opore. tai tara fire service
er belloon er jonno wait korte thaklo.
eri moddhe sada chamrar meye
puree mara gelo. kintu kalo meye
konorokom tike ache. fire service
bellon niye ashar por nigro meye
upor theke laf dilo kintu se beshi
mota houay belun chire rastay aghat
kheye mara gelo, mane kalo meyer
odokkhep porse.

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6. Ionic polymer and nonionic polymer:
On the basis of polarity polymers may be classified as
i. ionic and
ii. nonionic polymers Almost all natural polymers are non ionic polymers

vanga

✓ Ionic polymers: Polymers can also be synthesized into ionic one. The
examples of such polymers are ion exchange resins, which are used in the
modern technique of softening water.
✓ Water of almost 0 (zero) ppm hardness can be obtained by using cationic and
anionic exchange resin in the softening process.
✓ The common examples of ion exchange resins are-

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Department of Chemistry Bangladesh University of Engineering
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 7. Homopolymer and copolymer:
Polymers may again be classified into two other different classes such as

a) Homopolymer and
b) Co-polymer

(i) Homopolymer:
One
• When a polymer molecule consists of monomer units only then it is called
homopolymer.

• Polyethene, polypropylene, polystyrene. polyvinyl alcohol etc. are the

examples of homopolymer.

A-A A-A-A-A: Homopolymer

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 (ii) Copolymer:
When a polymer molecule consists of two or more different monomer units then it is
called copolymer.
▪ In majority of commercial co-polymers only two kinds of monomeric units are
found but in a few of them three different units are also found.
▪ Similar to the normal polymer copolymers may also be linear, branched or
cross-linked.
▪ In a co-polymer molecules monomers may be arranged at random or in a regular
manner.
▪ Copolymers of the former group are called irregular polymer whereas those of
latter group are called regular polymer. The structure of these polymers are
shown below:

a) Random co-polymer -A-A- B-A-B-B- A- (Irregular)

b) Alternating copolymer -A-B-A-B-A-B-A-B- (Rerular)

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 A block copolymer is a linear polymer with one or more long uninterrupted
sequences of each mer in the chain

A graft copolymer, on the other hand, is a branched copolymer with a

backbone of one type of mer and one or more side chains of another mer :

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 8. Stereospecific polymer:
❑ In such type of polymer chain, every alternate carbon atom is an
asymmetric carbon atom, that is, the alternate carbon atom C* carries four
different substituents, which are
a. –H,
b. R and
c. two polymer segments.
Hence each of these C* atoms is capable of providing a site for optical
isomerism, and each such site can exhibit either d-or l-type of isomerism,
depending on whether the group R lies below or above the plane of carbon chain.

❑ The regularity or the order in which the successive asymmetric carbon

atoms exhibit their d-or l-form gives rise to three different types of structures
in the polymer molecule.

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 9. Geometrical isomers
Geometrical isomers, are possible within repeat units having a double bond between
chain carbon atoms. Bonded to each of the carbon atoms participating in the double
bond is a side group, which may be situated on one side of the chain or its opposite.
Consider the isoprene repeat unit having the structure.

Cis-polyisoprene, is natural rubber. Trans-polyisoprene, sometimes called

gutta percha

➢ Gutta percha has properties that are distinctly different from natural rubber as a
result of this configurationally alteration.
➢ Conversion of trans to cis, or vice versa, is not possible by a simple chain bond
rotation because the chain double bond is extremely rigid.

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 Classification of inorganic polymer
Inorganic polymer may be classified as
(a) Homochain and
(b) Heterochain polymer.

a) Homochain polymer

Homochain polymer is the polymer in which polymeric chain consists of

single atoms. Most of organic polymers may be considered as the
homopolymer. In inorganic polymer sulphur and selenium have a high
tendency to form homochain polymeric compound.

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 b) Heterochain polymer:
In heterochain polymers, the backbone of the polymer chain
consists of two or more different atoms. The examples are
polysilicon dioxide, polysilicic acid, poly phosphoric acid etc.

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Department of Chemistry Bangladesh University of Engineering
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 Depending on the ultimate form and use, polymers may be
classified as-
i. Plastic,

ii. Elastomer

iii. Fiber and

iv. Liquid resin

(i) Plastic:

These are the polymers, which can be given shape of any hard and tough articles by
the application of heat and pressure. The examples of such polymers are poly vinyl
chloride, poly acryl amide, poly methyl methacrylate etc.

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 (ii) Elastomer:

These are rubber like substances, which deform on the application of load but
come back to their original shape on withdrawing load. That is, these polymers
readily undergo reversible deformation and elongation. Examples of
elastomers are natural rubber, synthetic rubber, silicon rubber etc.

(iii) Polymer Fibers:

Polymer fibers may be defined as the polymer which can be drawn into a
long filament like threads and whose length will be at least 100 times larger
of their diameter. Typical examples or such polymer fibers are nylon, terylene,
jute fiber etc. In these polymers inter particle forces are quite stronger.

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 (iv) Liquid resin:

These are the polymers, which are usually obtained in liquid or semisolid form.
These are used as adhesive particularly in paint and varnish industry. The
atahalo
examples of such polymers are epoxy resin, shellac etc. These polymers have got
sealant properties also.

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