POLYMER

STRUCTURE
AND PROPERTIES
Alsua, Melissa Joy D.
Realoza, Janshara B.
Sison, Felicia Chloe L.

poly = many mer = repeating units

substance consisting of large molecules that are
made of many small, repeating units called monomers,
or mers.

C C C C C C
H H H H H H
H H H H H H
Polyethylene (PE)
Cl Cl Cl
C C C C C C
H H H
H H H H H H
Poly(vinyl chloride) (PVC)
H H
H H H H
Polypropylene (PP)
C C C C C C
CH
3

H H
CH
3
CH
3
H
3
- most polymers are hydrocarbons


Saturated hydrocarbons


Each carbon singly bonded to four other atoms and no new
atoms may be joined without the removal of others that are
already bonded.

Example:

Ethane, C
2
H
6
Methane, CH
4

Propane, C
3
H
8
Butane, C
4
H
10

Pentane, C
5
H
12
Hexane, C
6
H
14

Unsaturated Hydrocarbons
Molecules that have double and triple covalent bonds.
each carbon atom is not bonded to the maximum
(four) other atoms
somewhat unstable can form new bonds

Double bond found in ethylene or ethene - C
2
H
4




Triple bond found in acetylene or ethyne - C
2
H
2



4
C C
H
H
H
H
C C H H
Isomerism
two compounds with same chemical formula can have
quite different structures

for example: C
8
H
18

normal-octane



2,4-dimethylhexane
5
C C C C C C C C H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H H
3
C CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
3
=
H
3
C CH
CH
3
CH
2
CH
CH
2
CH
3
CH
3
H
3
C CH
2
CH
3
( )
6

6
Polymers are substances that consist of very large
molecules called macromolecules that are made up of many
repeating subunits.

The molecular subunits that are used to synthesize
polymers are called monomers, and the reactions by which
monomers are joined together are called polymerizations.
Many polymerizations can be initiated by radicals.


7
When all the repeating units along a chain are of the same
type, the resulting polymer is called a homopolymer.

Chains may be composed of two or more different repeat
units, in what are termed copolymers.

monomers have an active bond that may react to form two
covalent bonds with other monomers forming a two-
dimensional chain-like molecular structure is termed
bifunctional.


8

In general, the functionality is the number of bonds that a
given monomer can form.


example, monomers such as phenolformaldehyde are
trifunctional; they have three active bonds, from which a
three dimensional molecular network structure results.
9
B ranched Cross-Linked Network Linear
secondary
bonding
10
Linear polymers
are those in which the repeat units are joined
together end to end in single chains.

These long chains are flexible and may be thought of
as a mass of spaghetti

For linear polymers, there may be extensive van der
Waals and hydrogen bonding between the chains.

Some of the common polymers that form with linear
structures are polyethylene, poly(vinyl chloride),
polystyrene, poly(methyl ethacrylate), nylon, and the
fluorocarbons.
11

The branches, considered to be part of the main-
chain molecule, may result from side reactions that
occur during the synthesis of the polymer. The chain
packing efficiency is reduced with the formation of side
branches, which results in a lowering of the polymer
density.

Those polymers that form linear structures may also
be branched. For example, high density polyethylene
(HDPE) is primarily a linear polymer, while low density
polyethylene (LDPE) contains short chain branches.
Branched polymers
12
Cross-linked
adjacent linear chains are joined one to another at
various positions by covalent bonds.

The process of cross-linking is achieved either
during synthesis or by a non-reversible chemical
reaction.

Often, this cross-linking is accomplished by additive
atoms or molecules that are covalently bonded to
the chains.

Many of the rubber elastic materials are cross-
linked; in rubbers, this is called vulcanization
13
Multifunctional monomers forming three or
more active covalent bonds, make three-
dimensional networks.

Actually, a polymer that is highly cross-linked
may also be classified as a network polymer.

These materials have distinctive mechanical
and thermal properties; the epoxies,
polyurethanes, and phenol-formaldehyde
belong to this group.
Network polymers
14
Molecular weight, M: Mass of a mole of chains.
Low M
high M
Not all chains in a polymer are of the same length
i.e., there is a distribution of molecular weights
15
x
i
= number
fraction of chains
in size range i
i i
n
M x M
w
i
= weight
fraction of chains
in size range i
M
i
= mean (middle)
molecular weight of
size range i
Number-average molecular weight
i i
w
M w M
Weight-average molecular weight
Degree of Polymerization, DP
DP = average number of repeat units per chain
m
M
DP
n

16
: follows as calculated is this copolymers for
unit repeat of weight molecular average where m
mol. wt of repeat
unit i
Chain
fraction
i i
m f m
17
Configurations used in reference to arrangements of
units along the axis of the chain, or positions that are
not alterable except by the breaking and then reforming
of primary bonds
Stereoisomerism denotes the situation in which atoms
are linked together in the same order (head-to-tail) but
differ in their spatial arrangement
C C
H
H
H
R R
H
H
H
C C
R
H
H
H
C C
R
H
H
H
C C
18
Types of stereoisomers
Isotactic configuration - all R groups on same side of chain
Syndiotactic configuration - R groups alternate sides
C C
H
H
H
R
C C
H
H
H
R
C C
H
H
H
R R
H
H
H
C C
Atactic configuration - R groups randomly positioned
C C
H
H
H
R R
H
H
H
C C
R
H
H
H
C C
R
H
H
H
C C
19
Geometrical isomerism
- Possible within repeat units having a double
bonds between chain carbon atoms.
Two kinds of geometrical isomers :
C C
H CH
3
CH
2
CH
2
C C
CH
3
CH
2
CH
2
H
cis
cis-isoprene
(natural rubber)
H atom and CH
3
group on
same side of chain
trans
trans-isoprene
(gutta percha)
H atom and CH
3
group on
opposite sides of chain
- two or more monomers
polymerized together
TYPES:
random A and B randomly
positioned along chain
alternating A and B
alternate in polymer chain
block large blocks of A units
alternate with large blocks of
B units
graft chains of B units
grafted onto A backbone

A B
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random
block
graft
alternating
Crystallinity is indication of amount of crystalline region in
polymer with respect to amorphous content



X-ray scattering and electron microscopy have shown that
the crystallites are made up of lamellae which,in turn, are
built-up of folded polymer chains
22
i) Chain length
ii) Chain branching
iii) Interchain bonding
Crystallinity occurs when linear polymer chains are
structurally oriented in a uniform three dimensional
matrix. Three factors that influence the degree of
crystallinity are:
Ordered atomic
arrangements involving
molecular chains

Crystal structures in terms
of unit cells

Example shown
polyethylene unit cell
23
Arrangement of
molecular chains in a
unit cell ofpolyethylene
Polymer Crystallinity
Crystalline regions
thin platelets with chain folds at faces
Chain folded structure

24
10 nm
Polymer Crystallinity
Polymers rarely 100% crystalline
Difficult for all regions of all chains to
become aligned
25
Degree of crystallinity
expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase.
crystalline
region
amorphous
region
Polymer Single Crystals
Electron micrograph multilayered single crystals
(chain-folded layers) of polyethylene
Single crystals only for slow and carefully controlled
growth rates
26
Semicrystalline Polymers
Some semicrystalline
polymers form
spherulite structures
Alternating chain-folded
crystallites and
amorphous regions
Spherulite structure for
relatively rapid growth
rates
27
Spherulite
surface
Photomicrograph Spherulites in Polyethylene
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Cross-polarized light used
-- a maltese cross appears in each spherulite
Source : Material Science and
Engineering 7e Callister
THANK YOU!!!