STRUCTURE OF POLYMERS

Introduction

Poly & mers Greek ; meros=part; polymer=many parts

Natural polymer derived from animals & plants wood, rubber, cotton,
wool, leather, and silk
Other natural polymers such as proteins, enzymes, starches, and cellulose
this group of materials and the development of numerous polymers
synthesized from small organic molecules.
Many of our useful plastics, rubbers, and ber materials are synthetic
polymers.
It can be produced inexpensively, and their properties can be managed to
the degree that many are superior to their natural counterparts.
In some applications metal and wood parts have been replaced by plastics
that have satisfactory properties and may be produced at a lower cost.
Most of polymers are organic in origin & based on hydrocarbon (H & C)

Hydrocarbon - HC

Hydrocarbon: H & C Intramolecular bonds are covalent

Each C atom has 4 e to participate in covalent bonding, every H
has 1 bonding e
Single covalent bondeach of 2 bonding atoms contributes 1 e;
CH4
Double & triple bond 2 C atoms share 2 & 3 pairs of e; C2H4
Saturated HC all single bond
No new atom may be joined without removal of atoms that are
already bonded
Double & triple covalent bonds unsaturated;
each C is not bonded to max atoms; other atoms are possible to
be bonded to the molecule

Acetylene
ethylene

 Some of the simple hydrocarbons

belong to the parafn family;
the chainlike parafn molecules include
methane (CH4), ethane (C2H6), propane
(C3H8), and butane (C4H10)
The covalent bonds in each molecule
are strong, but only weak hydrogen and
van der Waals bonds exist between
molecules, and thus these hydrocarbons
have relatively low melting and boiling
points.
HC comp with same composition but
different arrangement isomerism;
affect the properties
E.g. N-buthane & isobuthane

Polymer molecules
Large molecule built up by repetition of small, simple
chemical units
Because of their size macromolecules
Atoms are bound by covalent interatomic bonding
For C polymer C the backbone
Many times each carbon atom singly bonds to two
adjacent carbons atoms on either side
2 remaining valence of C may involve in side-bonding
with atoms/radical that are positioned adjacent to the
chain
Each of the two remaining valence electrons for every
carbon atom may be involved in side-bonding with atoms
or radicals that are positioned adjacent to the chain.

 Long molecules are composed of structural entities

called repeat units (Mers)
Monomer: small molecule from which a polymer is
synthesized
Hence, monomer and repeat unit mean different
things

The chemistry of polymer

molecules
At Tr and P C2H4-ethylene is gas
If the ethylene gas is polymerised under
appropriate conditions, it will transform to
polyethylene (PE), which is a solid polymeric
material.
This process begins when an active center is formed
by the reaction between an initiator or catalyst
species (R) the ethylene monomer:

 The polymer chain then forms by the sequential

addition of monomer units to this active growing
chain molecule.
The active site, or unpaired electron (denoted by
*), is transferred to each successive end
monomer as it is linked to the chain. This may be
represented schematically as follows:

 The nal result, after the addition of many ethylene

monomer units, is the polyethylene molecule;
This polyethylene chain structure can also be represented
as

Here the repeat units are enclosed in parentheses, and the

subscript n indicates the number of times it repeats.

 other chemistries of polymer structure are

possible.
For example, the tetrafluoroethylene monomer,
can polymerize to form polytetrafluoroethylene
(PTFE) as follows:

Polytetrafluoroethylene (having the trade name

Teflon) belongs to a family of polymers called the
fluorocarbons.

 the vinyl chloride monomer

is a slight variant of
that for ethylene, in which one of the four H atoms is replaced with a
Cl atom.
Its polymerization is represented as

leads to poly(vinyl chloride) (PVC)

Some polymers may be represented using the following generalized
form:

where the R depicts either an atom [i.e., H or Cl, for polyethylene or

poly(vinylchloride), respectively], or an organic group such as
CH3,C2H5, and C (methyl, ethyl, and phenyl).
For example, when R represents a CH group, the polymer is
polypropylene (PP).

MOLECULAR WEIGHT
Extremely large molecular weights are observed in polymers
with very long chains.
When all of the repeating units are the same homopolymer
Chain may be composed of 2 or more different repeat units
copolymer
During polymerization process, not all polymer chains grow the
same length, result in distribution of chain length/MW length
an average molecular weight is specied
the melting or softening temperature increases with increasing
molecular weight
At Tr polymers with very short chains (M ~100 g/mol) liquid;
~ 1000 g/mol are waxy solids (such as parafn wax) and soft
resins; Solid polymers (sometimes termed high polymers),
commonly have M ranging 10,000 - several million g/mol)

 Thus, the same polymer material can have quite

different properties if it is produced with a
different molecular weight.
There are several ways of dening average
molecular weight:
1)the number-ave MW,
2)the weight-ave MW, and
3)degree of polymerisation

1)The number-average MW

Dividing the chains into series

of size range
then determining the number
fraction of chain within each size
range.
Expressed as:

Mi=mean/middle MW of size
range i
xi = fraction of total number of
chain within the corresponding
size range

2) The weight-average MW
weight fraction of molecules
within various size ranges.
Calculated as:

Mi=mean MW within size

range i
wi =weight fraction of
molecules within the same
size interval

A typical molecular weight distribution along with these

molecular weight averages

3)Degree of
polymerization
DP Average chain size of polymer
DP average number of repeat units (mers) in
a chain
related to the number-average molecular
weight
Can be expressed as :

Mn & m = number average MW & repeat unit

(mer) MW

Example
Figures of MW distribution are for PVC.
Calculate a) number-average MW b) weightaverage MW & c) degree of polymerisation

a) Table for number-average MW

21,150 g/mol

 b) Table for weight-average MW

23,200 g/mol

c) PVC 2 C, 3 H & 1 Cl

Molecular Structure
Linear, branced, crosslinked,
network

LINIER POLYMERS
repeat units are joined end to
end in single chains
each circle represents a repeat unit
Melt on heating, flexible
Mechanical strength increases with
entangle chain

Example of Linier Polymer

Polyethylene
HDPE
PVC
Polystyrene
Nylon
fluorocarbon

BRANCHED POLYMERS

The branch considered to be part of the main chain

molecules
side-branch chains are connected to the main one
May result from side reactions that occur during the
synthesis
The chain packing efficiency reduces with formation of
side branches lowering polymer density
By changing T, the branched polymer can be hardened
or softened
Those polymers that form linear structures may also be
branched.
E.g. LDPE contains short chain branches.

CROSSLINKED POLYMERS

Adjacent linear chains are joined one to another at

various positions by covalent bonds
increase strength, reduce plasticity
Achieved during synthesis or by nonreversible
chemical reaction
Often, accomplish by additive atom/molecules that
are covalently bonded to the chains
The movement of adjacent chains is greatly
restricted, affected the mechanical properties to a
great extent
E.g. rubber elastic material

Networking polymer
Multifunctional monomers forming three or more active
covalent bonds, make three-dimensional networks
a polymer that is highly crosslinked may also be classied as a
network polymer.
These materials have distinctive mechanical and thermal
properties;
E.g: epoxies, polyurethanes, and phenol-formaldehyde
Polymers are not usually of only one distinctive structural type.
For example, a predominantly linear polymer might have
limited branching and crosslinking.

Thermoplastic &
Thermosetting
The response of a polymer to mechanical
forces at elevated temperatures is related to
its dominant molecular structure.
one classication scheme for these materials
is according to behavior with rising
temperature: Thermoplastics (or
thermoplastic polymers) and thermosets (or
thermosetting polymers)

Thermoplastic Polymers
Soften when heated (eventually liquefy), harden
when cooled reversible & may be repeated
Plastic & flexible properties
Formed at high T, cooled, remelted & reformed into
different shape without changing properties
On a molecular level, as the temperature is raised,
secondary bonding forces are diminished (by
increased molecular motion) so that the relative
movement of adjacent chains is facilitated when a
stress is applied.

 Overheat material decomposes, irreversible

degradation
Relatively soft
Most linear, some branches polymer with flexible
chains
Fabricated by simultaneous heat & pressure
Example: polyethylene, polystyrene, PVC,
poly(ethylene terephthalate

Thermosetting

Network polymers
Strong bonds, often formed by condensation
Permanently hard during formation when
heat applied
Do not softened/reshaped upon subsequent
heating loss of part of the molecule
Further heat burn/decompose
Generally harder, stronger & better stability
than thermoplastic
Most crosslinked, in that 10 to 50% of the
chain repeat units are crosslinked.
Only heating to excessive temperatures
causes severance of these crosslink bonds
and polymer degradation.
Ex: phenolic, vulcanized rubber, epoxies

Copolymers

Polymers with more than 1 repeat unit

Different type depends on method synthesis & repeat unit
type
Sequencing arrangement: random, alternating, block &
graft copolymer
1) Random copolymer random distribution of various
mers
E.g nitrile rubber

 2)

Alternating copolymer 4) Grafted copolymer

homopolymer side branches
2 mer units alternate chain
of one type may be grafted
position
to homopolymer main chain
that are composed of
different mer

3) Block copolymer
identical repeat units are
clustered in blocks along the
chain