Polymer Science

What are Polymers?

Polymers are composed of high molecular weight materials,
materials
macromolecules, formed by linking together of monomer molecules,
through chemical reactions known as polymerizations.
A polymer[ P] molecule is a single, high molar mass(M) molecule, i.e. a
macromolecule, consisting of a large number (n) of repeat units or
segments
g
[[S];
];
P = -[S]nMp = n.MS
A segment is not the same as the monomer(s) used in the preparation of
th polymer:
the
l
Eg.
Polyethylene(PE)

CH2=CH2
Monomer

CH2-CH2 n
repeat unit

 monomer must contain two or more bonding sites.

The number of bonding sites is referred to as functionality.
Monomers must have a functionality of two or higher to

be capable of linked together.

Eg. CH2=CH2 , NH2-(CH2)n-COOH , C6H5CH=CH2

Bifunctional monomers
Polyfunctional monomers

linear polymers
branched macromolecules

Eg. Glycerol CH2OH.CHOH.CH2OH

Linear Polymers

Branched Polymers

Homopolymers

A Polymer
P l
which
hi h contains
t i single
i l type
t
off repeatt units
it is
i referred
f
d
to as a homopolymer.
The repeat unit may contain one or more species of monomer
units.
units

Eg. Polyethylene, polypropylene, polystyrene, poly(ethylene terepthalalate)

Copolymers

A polymer derived from more than one type of repeat units is

referred to as a copolymer.
p y
Depending on the distribution of repeat units the copolymers
can further be grouped as random, alternating, block or graft
copolymers.
Eg. Styrene butadiene coplolymer, Acrylonitrile butadiene copolymer

Classification of Polymers
More than one criterion can be used as the basis for classification of polymers.

Eg.
g
Basis of Classification

Polymer Types

g
Origin

Natural, semi-synthetic,
y
synthetic
y

Mode of Formation

Addition, Condensation

Line Structure

Linear, Branched, Cross-linked

Tacticity

Isotactic, Syndiotactic, Atactic

Crystallinity

Non- crystalline, Semi-crystalline,

Crystalline

Thermal Response

Thermoplastic, Thermosetting

Application and Physical

Properties

Rubbers, Plastics, Fibres

Natural polymers : Eg. Natural rubber, natural silk,

cellulose, starch, proteins

Origin

Semi-synthetic polymers: Chemically modified

natural polymers. Eg.
Chlorinated, epoxidised,
p
or
cyclised natural rubber

Synthetic polymers: man made polymers. Eg. Polyethylene,

Polystyrene,
Polyvinylchloride, Polyesters

Chainreactionpolymers
(Addition polymers)
(Additionpolymers)

Mode of Formation

Eg. Polyethylene, polypropylene, polystyrene,

polybutadiene etc

Stepreactionpolymers
(Condensationpolymers)
Eg Nylon
Eg.
Nylon, Polyester

Linear polymers
( can be represented by lines)

Line structure

Branched polymers
(can be represented b
by lines with
ith short
or long branches of repeat units)

Network polymers
(polymer chains are interconnected as a net)

Tacticity
Vi
Vinyll polymers
l
th
thatt h
have single
i l substituents
b tit
t ((e.g. propylene)
l
) or
two unsymmetrical substituents (e.g. methyl methacrylate) have
pseudoasymmetric carbon atoms in the backbone.
Then there are many possible relative placements of the groups.
The most common three versions are;

Isotactic - all the substituents are on the same side

Syndiotactic - substituents are attached alternatively
Atactic - substituents are attached randomly

The different forms may have very different physical properties

eg. atactic polypropylene is a useless, gummy solid
isotactic polypropylene is a highly crystalline, tough plastic
that can even be made into fibers.

Crystallinity
Polymer molecules are very large so that they could not pack together
regularly and form a crystal.
It now is known that regular polymers may form lamellar (plate-like)
crystals with a thickness of 10 to 20 nm in which the parallel chains
are perpendicular to the face of the crystals.

These polymers are called crystalline polymers.

Polymer chains with branches or irregular pendant groups cannot

pack together regularly enough to form crystals.

These polymers are said to be amorphous.

amorphous

Thermal Response

Thermoplastic polymers: They can be softened or plasticized

repeatedly
p
y on application
pp
of thermal energy.
gy Eg.
g Polyethylene,
y y
,
polystyrene, polyesters, poly(vinyl chloride)

Thermosetting polymers: Thermosets become hard and rigid on the first

application of heat. Unlike thermoplastics, reheating will not weaken the
i t
intermolecular
l
l bonds
b d and
d the
th polymer
l
d
does
nott melt
lt again..
i Eg.
E Phenolic
Ph
li
resins, Epoxy resins, Urea/melamine resins

Application & Physical Properties

Rubbers: These polymers are characterized by long-range elasticity.
Mechanically they are rather weak and undergo high elongation even on
application
app
ca o o
of low
o sstresses.
esses They
ey e
exhibit
b tensile
e s e sstrengths
e g s in the
e range
a ge o
of
300-3000psi and elongation at break ranging between 300-1000%. Eg.
Natural rubber, synthetic rubbers

Plastics: These are usually much stronger than rubbers. They exhibit
tensile strengths ranging between 4,000-15,000psi and elongation at
breaks ranging
g g from 20-200%. eg.
g Polyethylene,
y y
polypropylene,
p
yp py
polystyrene

Fibres:
These are the strongest types of three different types of
polymers. Their tensile strengths are in the range of 20,000-150,00psi.
eg. Cotton, wool, silk, synthetic polyamides and polyester fibres and
acrylic fibres

Polymer
y
Nomenclature
There is no single nomenclature system. Difficulties are
associated with;

Tacticity

Copolymer arrangement

Structure irregularities

Imperfections

Variations in chain length

Methods
l

Source name (more common use)

n

Structure based (more systematic)

n

used in both source and structure names

Abbreviations and acronyms

n

emphasizes actual structure (polymethylene)

IUPAC, constitutional repeating unit

n

based on monomer name (polystyrene)

PMMA [poly(methyl methacrylate)]

Trade names
n

marketing and technological literature

Source Based (homopolymers)

SourceBased(homopolymers)
l

Use name of actual monomer

n
n

polymonomer, i.e. polyethylene

common names may be used for monomer
H2C

CH3

CH
H2C

styrene

CH

C CH2

CH3

CH3

isobutylene

isoprene

H2C CH
C N

acrylonitrile

Use ( ) when two words or substituents

n

H2C

poly(vinyl chloride), poly(1,2-difluoroethylene)

Use { [ ( ) ] } in cycle as needed

SourceBased(copolymers)
l

Infixes or connectives
n

-co- (unspecified arrangement), poly(A-co-B)

-ran- (Bernoullian distribution), poly(A-ran-B)

-alt- (alternating)

-per- (ordered sequence for >2 monomers)

poly(A-per-B-per-C)

-block- Polyacrylonitrile-block-polybutadiene

-graft- polyisoprene-graft-poly(methacrylic acid)

nonlinear blends
nonlinear,
blends, cross
cross-link,
link and net
network
ork
n

star- (prefix), -comb-, -blend-, net- (prefix)

poly(acrylic acid)-comb-polyacrylonitrile

StructureBased(homopolymers)
l

IUPAC nomenclature prevalent

n

complete repeating group (CRU) is named as a bivalent organic

group according to IUPAC

Identify, orient, and name the CRU

n

based on seniority and direction

1. heterocyclic rings (ring size over # of hetero)
2 H
2.
Heteroatom
t
t
(O,
(O S,
S N,
N P
P, Si)
3. carbocycles (unsaturated over saturated)
4 carbon chains
4.
poly[oxy(1-methylethylene)]

CH3

CH3

CH3

O CH CH2 O CH CH2 O CH CH2

Examples
1. Poly(1-acetoxyethylene) - structure
2. Poly(vinyl acetate) - source
1. Poly(but-1-ene-1,4-diyl)
2. Polybutadiene
y
1. Poly(1-cyanoethylene)
2. Polyacrylonitrile
1. Poly(methylene)
2. Polyethene;
y
p
polyethylene
y y
1. Poly[(2,5-dioxotetrahydrofuran3,4-diyl)(1-phenylethylene)]
2. Poly(maleic anhydride-alt-styrene)

CommonTradeNames
Selected examples
Crystalor

(polymethylpentene, Phillips)

Dowlex (LDPE/LLDPE, Dow)

Forar

(HDPE, Amoco)

Kevlar

(aramid fiber, DuPont)

Lexan

(polycarbonate, G.E.)

Lucite

(acrylic DuPont)
(acrylic,

Mylar

(poly(ethylene terephthalate), DuPont)

Nylon
y

((polyamides,
y
variations))

Olevac (polypropylene, Amoco)

Petrothene

(polyethylene, Quantum)

Saran

(poly(vinyl dichloride), Dow)

Teflon

(tetrafluoroethylene, DuPont)

CommonAbbreviations
Selected examples
ABS

(acrylonitrile butadiene styrene)

LLDPE (linear low density polyethylene)

PA66

[polyamide (Nylon) 66]

PC

(polycarbonate)

PET

[poly(ethylene terephthalate)]

PMMA

[poly(methyl methacrylate)]

PS

(polystyrene)

PVC

[poly(vinyl chloride)]

TP

(thermoplastic elastomer polyolefin)

Structure vs Properties

It is not possible to predict mechanical properties of

polymers just by the chemical structure of repeat
unit(s).
chemical structure of individual segments contributes
partly
y or indirectlyy to mechanical p
properties.
p
onlyy p
Direct role is more often is played by the
supramolecular structure.
structure i.e.
i e physical arrangement of
chain molecules with respect to each other.

Polymer Chain Structure

The physical structure of a polymer chain is an important

factor as it determines the macroscopic properties of the
polymer.

JJustt because
b
a polymer
l
i synthesized
is
th i d from
f
a pure
monomer, where all the molecules are initially identical,
does not mean that the final product consists of chains of
regularly arranged units.

Two terms known as configuration and conformation are

used to describe the structure of a polymer.

Polymers can exist in various conformations and various

configurations.

Conformation
Two polymers which differ only by rotation about single bonds are said
to be two different conformations of that polymer.

Configurations

Two polymers which have the same chemical composition

but can only
y be made identical by
y breaking
g and reforming
g
bonds are said to be to configurations of that polymer

It is not possible to turn polymers in different configuration

states into superimposable polymers by rotating about
single bonds

Stereoregularity is the term used to describe the

configuration of polymer chains, They can be either
cis/trans isomers or stereo isomers depending on their
structure.
structure

These are two different configurations of 1

1,2
2 dichloroethene
dichloroethene.
This occurs when there is un-saturation in the polymer chain

If the polymer chain contains chiral centers or asymmetric centers

th stereo
then
t
i
isomers
are possible.
ibl These
Th
stereo
t
i
isomers
are different
diff
t
configurations of polymers.
Eg polystyrene
Eg.

IsotacticSyndiotacticAtactic

Isomerism in polymers
An asymmetric monomer would produce polymers with a
variety of microstructures consisting of various types of
i
isomers.
Th mostt important
The
i
t t types
t
are;
1 Sequence isomers
1.
2. Configurational isomers
3 Structural isomers
3.

Configurational Isomerism

Configurational isomers are isomers in which their atoms are

linked together in the same order but in different spacial
arrangements.
arrangements

Therefore they have the same molecular formula.

The same atoms are arranged in the same order but with
different orientations in space.

Configurational isomerism may be subdivided into two sub

groups.
(
isomerism))
1. Geometrical isomerism(cis-trans
2. Stereoisomerism

Geometrical isomerism(Cis-trans isomerism)

These isomers occur when;
(i) there
th
i restricted
is
t i t d rotation
t ti
somewhere
h
i a molecule.
in
l
l Eg
E
carbon double bond.

carbon
b

(ii) two different groups on the left-hand

left hand of the bond & two different
groups on the right hand end.

These are not isomers

But when there is a carbon carbon double bond the two molecules are
not the same

Properties of cis/trans isomers of a given compound are very different.

This type of isomerism could be found in some polymeric materials particularly if

they are produced from conjugated dienes
dienes.
eg. polymerization of isoprene.
Cis & Trans isomers of naturally occurring polyisoprenes.

Cis I,4 polyisoprene

Trans 1,4 isoprene

Polyisoprene from Hevea brasiliensis

cis isomer
has a amorphous structure
rubbery material

Polyisoprene from Gutta Percha

trans isomer

Natural rubber is high molecular weight almost 100% cis1,4polyisoprene,

but many synthetic elastomers have various proportions of isomers.
The average composition of the chains varies with the temperature of
polymerization, whether or not a catalyst has been used, and so on.

very
e y regular
egu a sstructure
uc u e
Crystalline
Plastics material

Stereoisomerism

Isomers which are mirror images of each other but do not

superimpose on each other.
The requirement for stereoisomerism is the attachment of 4
different atoms or groups of atoms to a single carbon atom(chiral
center).

Head to Tail

Head to Head

If the successive
s ccessi e configurations
config rations of the asymmetric
as mmetric carbons are
regular then the polymer is said to be stereo regular

 In a stereoregular polymer chain the substituent groups (Z) attached to the

asymmetric carbons will be located above or below the plane defined by the
carbon chain.
Three configurational isomers can be identified for such polymers.

all the substituents lie on

one side of the chain

substituents alternate from

one side to another in a
regular manner

a random arrangement
of ssubstituent
bstit ent groups
gro ps

 Manyy common and useful p

polymers,
y
, such as p
polystyrene,
y y
, polyacrylonitrile
p y y
and
poly(vinyl chloride) are atactic as normally prepared.
Using specific catalysts stereoregular polymers can be obtained

Polymer

Tg atactic

Tg isotactic Tg syndiotactic

PP

20 C

0 C

8 C

PMMA

100 C

130 C

120 C

 The properties of a given polymer will vary

considerably
id bl with
ith itits ttacticity.
ti it
Atactic polypropylene is useless as a solid
construction material
material, and is used mainly as a
component of adhesives
In contrast,
contrast isotactic polypropylene is a high-melting
solid (ca. 170 C) which can be molded or machined
into structural components.

Structural isomerism
In structural isomerism, the atoms are arranged in a completely
different order. eg. Butane,C4H10

Pentane, C5H12, has three structural isomers.

Several structural isomers are formed during the polymerization of

diene monomers.
Eg. Polymerization of isoprene

1,2 & 3,4 & 1,4 polymers are structural

isomers of polyisoprene.
Cis 1,4 & trans 1,4 isomers are geometrical
isomers of 1,4 polyisoprene.
1,2 and 3,4 isomers could lead to Isotactic,
syndiotactic, or atactic structures.
Also all the forms could show sequence
isomers depending
p
g on the bonding
g as H-H,,
H-T, T-T .

I.

Activity
Draw the structure of the repeat units of the polymers obtained in the
polymerization of the following monomers;
I.
CH2=CHCOOH
II. CH2=C(CH3)COOCH3
III. CH2=CHOCOCH3
Give the name(sources based) of each polymer produced

II Which of the following monomers can form Isotactic polymers.

I
I.
CH2=CHCH=CH2
II. CH3C(CH3)=CH2
III. CH(CH3)2CH=CH2
Draw the structures of syndiotactic isomers of those polymers
III Draw the structures of
I.
The syndiotactic polymers produced from 1,2 enchainment of
isoprene
II. Isotactic poly(3,4 isoprene)
IV. What configurational isomers are possible from the polymerization of
CH2=CHCH=CH
CHCH CH2
Draw the structures of all the possible isomers.

Polymer Morphology

Morphology is the science of form and structure. It provides the link

between the structure and bulk properties.
As applied to polymers, morphology involves the study of the
arrangement of polymer molecules in the bulk polymer.
Behaviour of most small molecules can be explained explained in
terms of 3 states. i.e. solid, liquid, gas
As the Polymers are large molecules with strong intermolecular
forces and entangled chains, they do not have a vapor phase and
they decompose before the temperature goes high enough to form
a vapour.
vapour
The polymer molecules are so long and it is difficult to form large
crystals as in the solid phase of most small molecules.
molecules

Therefore the behavior of polymers can be explained

in terms of two phases;
Cr stalline phase
Crystalline

-------- ordered structure

str ct re

Amorphous phase -------- unordered structure

Although a few polymers may be crystalline and a few polymers
may be completely amorphous, most of the polymers are partially
crystalline.

Unfold structure

Folded Structure
E t
Entangled
l d St
Structure
t

Photomicrograph of spherulite structure of polyethylene

Amorphous Polymers
Polymer chains with branches or irregular pendant groups can
not pack together regularly enough to form crystals. These
polymers are said to be amorphous.

Amorphous polymers are usually less rigid, weaker and more easily
deformed. They are often transparent and more affected by solvent
penetration.

Semi-crystalline polymers

These polymers have both crystalline and amorphous regions.

Semi-crystallinity is a desirable property for most plastics because
they combine the strength of crystalline polymers with the flexibility of
amorphous.
Semi-crystalline polymers can be tough with an ability to bend
without breaking.

Different polymers crystallize to different extents and therefore possess

different properties.
properties
Eg.

Highly Crystalline

Highly Amorphous

Polymers

Polymers

Isotactic polypropylene

Poly(methylmethacrylate)

Syndiotactic polypropylene

Atactic polystyrene

Nylon

Polyisoprene

Kevlar

Polybutadiene

Polyketones

Polycarbonate

Factors affecting crystallization

1. Polymer Structure;
i) Chain length
ii) Chain
Ch i branching
b
hi
2. Inter-molecular forces

Polymer
o y e St
Structure;
uctu e;

To crystallize a polymer chain must be linear.

Limited crystallization may occur if a small number

of branches are present.

Crystallization
C
t lli ti is
i favored
f
d by
b the
th stereo
t
regularity
l it off
the polymer chain

Linear polyethylene This is made possible by the planar zig-zag structure

easily assumed by the molecule
molecule.

Normal polystyrene is atactic with no regular order in the position of

the benzene rings along the chain.
The irregularity prevents the chains from packing closely to each
other.
Atactic polystyrene, is amorphous. It is comparatively soft, low melting,
and becomes swollen in solvents.

In syndiotactic polystyrene the benzene rings are on alternate sides

of the chain. This allows the chains to pack into crystals.

Syndiotactic polystyrene is crystalline. It is rigid, high melting, and not

penetrated readily by solvents

Syndiotactic polystyrene

Degree of Polymerization

Relatively short polymer chains form crystals more readily than

l
long
chains,
h i
b
because
th long
the
l
chains
h i tend
t d to
t be
b more tangled.
t
l d

High crystallinity generally means a stronger material, but low

molecular weight polymers usually are weaker in strength even if
they are highly crystalline.

Low molecular weight polymers have a low degree of chain

entanglement, so the polymer chains can slide by each other
and cause a break in the material.

Intermolecular Forces

Crystallinity is favored by strong interchain forces

The p
presence of p
polar and hydrogen
y g
bonding
g g
groups
p favors crystallinity
y
y
because they make possible dipole-dipole and hydrogen bonding
intermolecular forces.

A polyester,
polyester such as poly(ethylene terephalate),
terephalate) contains polar ester
groups.

Dipole-dipole forces between the polar g

groups hold the PET molecules in
strong crystals.

Crystallinity in poly(ethylene terephalate) also is favored by the structural

regularity of the benzene rings in the chain
chain.

The benzene rings stack together in an orderly fashion.

Pendant Groups

Regular polymers with small pendant groups crystallize more readily than do
polymers with large, bulky pendant groups.

Poly(vinyl alcohol) (PVA) is made by the hydrolysis of poly(vinyl acetate)

(PVAc).

PVA
PVAc

PVA crystallizes more readily than PVAc because of the bulky acetate groups
in PVAc.

The -OH groups in PVA also form strong hydrogen bonds