ORGANIC CHEMISTRY

Macromolecules
CONTENTS
 Introduction
 Types of Macromolecules
 Synthetic Polymers
 Addition Polymerization
 Formation of Poly(ethene)
 Types of Poly(ethene)
 Some More Addition Polymers
 Condensation Polymeriztion
 Formation of Esters
 Formation of Polyester
 Formation of Nylon
 Natural Polymers – Introduction
 Formation of Proteins
 Formation of Fats
 Formation of Carbohydrates
 Comparison of Synthetic and Natural Polymers
 Question Time Exit
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1- Covalent Giants 2- Polymers

Polymerization
Introduction
 Process of joining small molecules (monomers) to form large molecules,

 Poly means ‘many’ and meros meaning ‘parts’,

 Number of monomers may vary from 50 to 50,000

 General equation can be represented as:

nM → (M)n
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Types
Polymers

Natural Synthetic

Condensation Addition
Polymers Polymers
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Synthetic Polymers

Addition Polymerization
(the linkage of un-saturated monomers to form a polymer)

 Contain same type of monomer

 no by-products formed

 most likely raw materials are alkenes and alkynes

 Examples : Poly(ethene), polystyrene, polyvinyl chloride (PVC), etc.

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Addition Polymerization
Formation of Poly(ethene)
Ethene
H H H H H HH H
C C C C C C C C
H H H H H HH H

H H H H H H H H
H H H H H HH H
C C C C C C C C
H H H H H H H H H H H HH H H H
H H
C C
H H n
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Types of Poly(ethene)

H
High D
Density P E
Poly(Ethene) L
Low D
Density P E
Poly(Ethene)
100 oC Temperature, atmospheric 180 oC Temperature, ~100atm.
pressure and a complex catalyst pressure and some oxygen
► It can not be cut easily ► It can be cut easily

► Being hard, it does not shatter ► Being soft, it can be shattered

► It can not be bent easily ► It can be bent easily

► It is more dense than water and ► It is less dense than water and
sinks floats over it.

► It can not be softened by heating ► It can be softened by heating

► When burnt gives sooty flames with ► When burnt gives smell of burning
waxy smell. candles..
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Some More Addition Polymers
Tetra-Fluoro
Propene Vinyl Chloride Acrylonitrile
ethene
CH3 H Cl H F F CN H
CH3 H Cl H F F CN H
C C C C C C C C
H H H H H H H F F F H H H
H F H

n n n n

Polyvinyl chloride Poly tetrafluoro Polyacrylonitrile

Poly-Propene
(PVC) ethene (Teflon) (acrilan)
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Some More Addition Polymers
Methyl methacrylate
Phenyl ethene (styrene)

C6H5 H COOCH
COOCH3 3 H
C6H5 H H
C C C C
H H H H H H H
H

n n

Polyphenyl ethene Polymethyl methacrylate

(polystyrene) (perspex)
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Synthetic Polymers

Condensation Polymerization
(the linking of monomers with the elimination of a simple molecule)

 Contain different types of monomers

 small molecules formed as by-product, e.g. H2O, SO2, H2S, etc.

 most are replications of natural condensation polymers

 Examples : Nylon, Terylene, etc.

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Condensationtion Polymerization
Formation of Ester

H O H H
| || | |
Reactants: H – C – C─ O─ H
| + H – O –C – C – H
| |
H H H

Products: +
Ethyl ethanoate Water
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Condensation Polymerization
Formation of Poly(ester)

Butane dioic acid Butane diol Butane dioic acid Butane diol
O H H O H H H H O H H O H H H H
|| | | || | | | | || | | || | | | |
–C–C–C–C–
HO–C–C–C–C–O H H–O– –C–C–C–C–
–O–H HO–C–C–C–C–O H H–O– –O–H
| | | | | | | | | | | |
H H H H H H H H H H H H

Ester
Linkage

Butyl butanoate
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Condensation Polymerization
Formation of Nylon
Butane dioic acid Butane diamide Butane dioic acid Butane diamide
O H H O H H H H O H H O H H H H
|| | | || | | | | || | | || | | | |
–C–C–C–C–
H–O–
H–O–C–C–C–C–O–H
–O–H H–
H–N–C–C–C–C–N–H
–N–C–C–C–C–N–
–H H–O–
H–O–C–C–C–C–O–H
–C–C–C–C–
–O–HH–
H–N–C–C–C–C–N–H
–N–C–C–C–C–N–
–H
| | | | | | | | | | | | | | | |
H H H H H H H H H H H H H H H H

Amide linkage

Nylon-4,4
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NATURAL POLYMERS

⌂ Found mainly in food-stuff

⌂ Contain compounds like proteins, fats, carbohydrates, etc.,

⌂ Complex compounds broken into smaller units by enzymes

⌂ Broken with the help of water molecule, the process called ‘hydrolysis’

⌂ Reformed by the action of other enzymes

⌂ Proteins have been replicated synthetically in making of nylon

⌂ Fats replicated in the formation of polyester

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NATURAL POLYMERS
(Formation of Proteins)
Amino acid ‘A’ Amino acid ‘B’ Amino acid ‘A’ Amino acid ‘B’
O O O O
|| || || ||
H–
H–N–
–N– ▓▓▓ –C–
–C–O–H
–O–H H–N–
H–
–N– –C–O–H
–O–H H–
–C– H–N– –O–H H–
–N– ▓▓▓ –C–
–C–O–H –N–
H–N– –C–
–C–O–H
–O–H
| | | |
H H H H

Amide linkage (also called the peptide linkage)

Structure of Proteins
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NATURAL POLYMERS
(Formation of Fats)
Carboxylic acids + Alcohol (glycerol) A Molecule of Fat Water

O
||
–O–H
C– H–
–O–CH2
+ O
||
C–
–O–H + H–
–O–CH +
+ O
||
C–
–O–H H–
–O–CH2

These processes are reversed during hydrolysis, when enzymes break down
the large fat, protein and carbohydrate molecules in the presence of water and
they yield the reactants, i.e. carboxylic acids + alcohols (from fats), amino acids
(from proteins) and glucose units (from carbohydrates).
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NATURAL POLYMERS
(Formation of Carbohydrates)
Glucose Glucose Glucose Glucose
HOH2C O
|
H–
H–C–O– ▓▓▓
H––CO–H
–OH H–
–O – –O–H
– O–H –O– ▓▓▓ – O–H H–
H– –O – –O–H
– O–H

H H
HO– C OH C –OH
|
C
|
H
Glycosidic linkage

Structure of Carbohydrates
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Similarities between Natural and Synthetic Polymers
Fats Polyester
O
||
–O–CH2
C– O H H O H H H H O H H O H H H H
O || | | || | | | | || | | || | | | |
|| O–C–C–C–C–O –C–C–C–C–O–C–C–C–C–O –C–C–C–C–
C–
–O–CH | | | | | | | | | | | |
H H H H H H H H H H H H
O
||
–O–CH2
C– Ester Linkage

O O O O
|| || || ||
Proteins –N– ▓▓▓ –C–
–N– –C–
–N– ▓▓▓ –C–
–N– –C–
| | | |
H H H H
Amide Linkage
O H H O H H H H O H H O H H H H
|| | | || | | | | || | | || | | | |
Nylon –N–C–C–C–C–N–
–C–C–C–C– –N–C–C–C–C–N–
–C–C–C–C–
| | | | | | | | | | | | | | | |
H H H H H H H H H H H H H H H H
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QUESTION TIME

In the presence of a catalyst, propene reacts and

produces a soft, white solid. This reaction is:

a) Substitution

b) addition

c) polymerization

d) hydrolysis
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QUESTION TIME

Q1. What is the raw material for the manufacture of

Nylon?
ANS: Dicarboxylic acids and diamides

Q2. Which natural polymers are the ‘Nylons’ a replica

of?
ANS: Proteins