Introduction to polymers

Dr. Tan Suk Fei (Sophie)

Pharmaceutical Chemistry Unit
School of Pharmacy
Management & Science University
Introduction to polymer Keyword

• Poly: Greek word “Many”; Mer: unit/parts

• Polymer: Polymer is a large molecule that

comprises repeating structural units joined by
the covalent bonds
• Monomer: The small molecule or repeating unit
of the building block in the the structure of
polymer

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 Polymer
• Large size (Large MW)
• Non volatile
• Chains becomes entangled

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 Introduction to polymer Keyword

• Polymerisation: Chemical reaction in which more

than 2 of 1 or more than 1 type of substance
combine together to form a molecule of high
molecular weight.

• Degree of Polymerization: Number of monomer

or repeating unit (n) in the polymer chain is called
degree of polymerization (DP)

Degree of polymerisation = Average molecular weight of polymer

Weight of repeating unit.

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Cross-link: Chemical bond between the polymers
other than bonding at the end of the polymer

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 Cross-linking
• Important in determining the physical
properties:
– ↑ cross-linking, the molecular weight of
polymer ↑
– ↑ cross-linking, the solubility of polymer ↓
– ↑ cross-linking, the ability of polymer to
absorb solvent ↓

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Polymer with few cross-link will produce a gel
polymer
- Insoluble in solvent
- Swell upon contact with solvent ( ↑ability o f
the polymer to absorb the solvent)

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Introduction to polymer Keyword
Difference between monomer, repeating unit & polymer

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 Polymer based on source
• Natural polymer
– Protein
– Starch
– Cellulose

• Synthetic polymer
– Plastic

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 Polymerisation process

Chain-growth polymerization (Addition)

Step-growth polymerization (Condensation)

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 ADDITION POLYMERIZATION
▪ Definition: The process where more than 2 atoms are
joined without losing any small molecules.
▪ Also known as chain-growth polymerization.
▪ This type of polymerization are usually exothermic.
▪ Monomers react to form a polymer without forming by-
product but by breaking its unsaturated bond.
– GENERAL REACTION:
n [CH2=CH] → [-CH2-CH-]n
| |
Y Y

Where Y can be atom or molecule:

H (Ethylene),CH3 (Propylene), Cl (Vinyl Chloride), C6H5, (Sterene),
CN (Acrylonitrile)

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 Quiz
• Write the polymer for:
• Write the name of this polymer

Polydibromoethane
Poly(dibromoethene)

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 ADDITION POLYMERIZATION

– Addition polymerization is usually carried out in

the presence of small quantity of substance
called Initiators.

– E.g.-Zeigler-Natta catalyst, potassium

persulphate , dibenzoyl sulphat e.

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 MECHANISM OF ADDITION POLYMERIZATION
{FREE RADICLE REACTION MECHANISM}

➢Free Radical Mechanism of chain

reaction involves 3 stages namely
I. Initiation
II. Propagation
III. Termination

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1. Generation of free radical : SCHEMATIC REPRESENTATION
•
• R - Free radical
I → 2R E.g. I → CH2=CH2 M - Unsaturated Monomer
2. Initiation :
• •
R + M → RM 1

3. Propagation :
• •
RM + M → RM
1 2

RM • + M → RM •
2 3

•
RM + M → RM
(x–1) x

• •
RM + M → RM
(y–1) y

4. Termination :
RM• + RM • → RM (COUPLING)
x y x+y

RM• + RM • → RM + RM (DISPROPORTIONATION)
x y x y

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DISPROPORTIONATION

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Termination
▪ By coupling (by the combination of two radicals)
R-(CH2-CH2)X-CH2-CH2• +•CH2-CH2-(CH2-CH2)Y-R

R-(CH2-CH2)X-CH2-CH2-CH2-CH2-(CH2-CH2)Y-R

▪ By disproportionation (a double bond is formed

whereas one of H atom is transferred to another)
R-(CH2-CH2)X-CH2-CH2 + R-(CH2-CH2)Y-CH2-CH2
• •

R(CH2CH2)X-CH2-CH3 + R(CH2CH2)Y-CH=CH2

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MECHANISM OF ADDITION POLYMERIZATION
OF POLY-ETHYLENE
• Synthesis of poly-ethylene -(CH -CH )- from
2 2 n

• Ethylene, CH =CH using di-benzoyl peroxide

2 2

(C H COO) as the initiator

6 5 2

n CH =CH → -(CH -CH )- n

2 2 2 2

(C6H5COO)2

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 CONDENSATION POLYMERIZATION
Definition: A process where 2 types of monomers containing functional
groups are joined together and lose a small molecule unit such as
H20 and HCl.

Polymers whose repeating units are joined together by functional units

such as ester (-OCO-), amide (-NHCO-), urethane (-OCONH-),
sulfide (-SO2-) and other linkages.

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 CONDENSATION POLYMERIZATION

• Self addition of several bifunctional

monomer to each other takes place
accompanying elimination of simple
molecules like H2O,NH3 & HCl
• General reaction:

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E.g..
❖Terylene is obtained by condensing
terpthalic acid [HOOC-C6H4-COOH]
with ethylene glycol [HO-C2H4-OH]
❖Nylon is made by the condensation of
adipic acid [HOOC-(CH2)4-COOH] with
hexamethylene diamine [NH2-(CH2)6-
NH2]

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E.g..
❖Terylene is obtained by condensing
terpthalic acid [HOOC-C6H4-COOH]
with ethylene glycol [HO-C2H4-OH]
❖Nylon is made by the condensation of
adipic acid [HOOC-(CH2)4-COOH] with
hexamethylene diamine [NH2-(CH2)6-
NH2]

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 They are NOT the same..
POLYMERISATION FOUNDER Based on type of Based on type of
products reaction
mechanism
Addition Wallace a polymer only -
Hume (addition)
Condensation Carothers a polymer and a -
(1929) molecule with a low
molecular weight side
product (ie: water)
Step-growth Paul Flory - by functional groups
Chain-growth (1953) - by free-radical or ion

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 EXAMPLE
Polyurethane • addition polymerization because
its polymerization produces no
small molecules.
• reaction mechanism corresponds
to a step-growth polymerization.

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STEP-GROWTH (E.G. CONDENSATION) VERSUS CHAIN-GROWTH (E.G. FREE RADICAL) POLYMERIZATION

Step-Growth Chain-Growth

During propagation, only monomers react to

WHERE TO REACT the “active site” at the end of the growing
chain.

MONOMER IS USED Large quantities of monomers are consumed early

SHARPLY OR STEADILY in the reaction.

There are two distinctive mechanisms during

polymerization; these are initiation and
ANY MECHANISM
propagation. In most cases there is also a
termination step.

The reaction proceeds rapidly at the beginning but

HIGH MW POLYMER CAN the molecular weight increases only slowly and
ONLY BE ATTAINED AT / high MW's are only attained at the end of the
WITH…. process
by long oligomers reacting with each-other.

TIME NEEDED FOR

Long reaction times have high degrees of
SYNTHESIS OF LONG (HIGH
conversion but do not affect (much) the
MOLECULAR WEIGHT)
(average) molecular weight.
POLYMERS.

The mixture contains primarily monomers

THE RANGE MOLECULAR
and polymers, and only small amounts of
WEIGHT OF THE SPECIES
growing polymer chains;
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With free radical help

Only with functional group

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