Chapter 3 Polymers

1. Introduction
• mer means “unit.” Thus, the term polymer means
“many units”. Polymers consist of chains of molecules.
• The chains have average molecular weights that range
from 10,000 to more than one million g/mol.
• Plastics are composed principally of naturally
occurring and modified or artificially made polymers
often containing additives such as fibers, fillers,
pigments, and the like that further enhance their
properties.

1
• Polymer macromolecules are composed of
structural entities called repeat units, which are
successively repeated along the chain.
• The term monomer refers to the small molecule
from which a polymer is synthesized.
• Monomer and repeat unit mean different
things, but sometimes the term monomer or
monomer unit is used instead of the more proper
term repeat unit.

2
Đơn vị cơ sở (Repeat unit)

3
4
5
2. Classification:

Polymers are classified in several ways: by how the

molecules are synthesized, by their molecular structure,
or by their chemical family.

 One way to classify polymers is to state if the polymer

is a linear polymer or a branched polymer

6
Most polymers are organic, meaning that they are
carbon-based; however, polymers can be inorganic
(e.g., silicones based on a Si-O network)
A better method to describe polymers is in terms of
their mechanical and thermal behavior.

7
 Thermoplastics are composed of long chains produced
by joining together monomers; they typically behave in a
plastic, ductile manner. The chains may or may not have
branches. Individual chains are intertwined.
There are relatively weak van der Waals bonds between
atoms of different chains.
The chains in thermoplastics can be untangled by
application of a tensile stress.
Thermoplastics can be amorphous or crystalline.
Upon heating, thermoplastics soften and melt. They are
processed into shapes by heating to elevated temperatures.
Thermoplastics are easily recycled.
Examples: polypropylene, Teflon (PTFE)

8
 Thermosetting polymers are composed of long chains
(linear or branched) of molecules that are strongly cross-
linked to one another to form three-dimensional network
structures.
Thermosets are generally stronger, but more brittle, than
thermoplastics.
Thermosets do not melt upon heating but begin to
decompose. They cannot easily be reprocessed after the
cross-linking reaction has occurred, and hence, recycling is
difficult.
Examples: epoxies, phenolics.

 Elastomers are known as rubbers. They sustain elastic

deformations greater than 200%.
These may be thermoplastics or lightly cross-linked
thermosets.
9
The polymer chains consist of coil-like molecules that can
reversibly stretch by applying a force.
Polymerization is the process by which small

molecules consisting of one unit (known as a

monomer) or a few units (known as oligomers)

are chemically joined to create these giant

molecules.

Polymerization normally begins with the

production of long chains in which the atoms are

strongly joined by covalent bonding. 10

3. Polymerization:

Polymerization by addition and condensation are

the two main ways to create a polymer.

The polymers derived from these processes are known

as addition and condensation polymers, respectively.

11
 Addition Polymerization
Addition polymers form:
•when unsaturated carbon (organic) molecules
react to form a long chain polymer molecule
•and no small molecules or atoms are eliminated
during the reaction

The general reaction can be represented as:

where R and R' can represent hydrogen atoms,

halogen atoms, alkyl or other carbon-containing
side chains. 12
 Condensation Polymerization
Condensation polymers form:
• when bifunctional monomers react to form a long
chain polymer molecule
• small molecules, such as water, are eliminated
during the reaction
Polyesters, polyamides, proteins and polysaccharides
such as cellulose, are all examples of condensation
polymers.

13
Polyesters form when the -OH functional group of one
monomer reacts with the -COOH functional group of another
monomer.
An ester link (-COO-) is formed between monomers during
the reaction.
H2O is eliminated in the reaction.
General reaction between a dicarboxylic acid and a diol:

14
4. Additives

15
5. Polymer structure

a) Linear chain

Polyethylene  : 109.5-120o

16
b) Network structure

17
18
 c) Polymer crystallinity
The crystalline state may exist in polymeric materials. However,
because it involves molecules instead of just atoms or ions, as with
metals and ceramics.
Polymer molecules are often only partially crystalline (or
semicrystalline), having crystalline regions dispersed within the
remaining amorphous material.

19
d) Bonding in polymer structure

 Bonding in a chain: covalent bonds: , 

 Bonding between chains: Van der Waals,

hydrogen bonds, disulfur crosslinking

20
 DEGREE OF POLYMERIZATION
 Polymers, unlike organic or inorganic
compounds, do not have a fixed molecular weight.
 For example, polyethylene may have a molecular
weight that ranges from 25,000 to 6 million!
 The average length of a linear polymer is
represented by the degree of polymerization, or
the number of repeat units in the chain.

21
 e) Average molecular weight

 We can define an average molecular weight in two ways.

 Weight average molecular weight

22
 Number average molecular weight

23
 Example:

24
25