Course Title: Organic Chemistry -II
Course Code: CHEM-103(TXE)
Chapter: Polymerization
Polymerization
Polymer: When a lots of small, reactive molecules are joined together to make a long chain giant
macromolecules, the product is known as polymer
Monomer: The small molecules from which polymer is formed called monomers.
Repeat Unit: It is the simplest part of the polymer which is repeated many times to form the polymer
Lots of ethenes poly (ethene)/polythene
n CH2=CH2 ( CH2CH2 )n
Here
Monomer: CH2=CH2
Repeat Unit: CH2CH2
Polymer: (CH2CH2) n
Addition polymer
The linking together of unsaturated monomers to form a single long chain molecule known
as addition polymer
Polythene from ethene is a well-known example of addition polymer
nCH2=CH2 (CH2CH2)n
Where double bond in ethene ‘open up’ and neighboring molecules join end to end
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Poly (ethene) comes in two types
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Low density poly (ethene) (LDPE)
Mainly used as a thin film to make polythene bags.
Its flexible ,less strong
High density poly (ethene) (HDPE)
used to make plastic bottles
greater strength, rigid
Addition Polymerization Reaction
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(i) Ethene [CH2=CH2] to poly (ethene)
(ii) Propene [CH3-CH=CH2] to poly propene
(iii) Chloroethene (Vinyl Chloride) [CHCl=CH2] to poly vinyl chloride (PVC)
(iv) Styrene [C6H5CH=CH2] to polystyrene
(v) Tetrafluoroethene (TFE) to poly tetrafluoroethene
Polymer chain showing more than one repeat unit
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Name of monomer Structure of monomer
2-methylprop-1 en
Chloroethene
OR
Vinyl Chloride
Phenylethene
OR
Styrene OR
But-2-ene
Propenamide
Ethenol
Draw the repeat unit of the following polymers
(i) Poly (ethene)
(ii) poly(propene)
(iii) poly(chloroethene)/PVC
(iv) (poly)tetrafluoroethene
(v) Polyethenol
(vi) Polypropenamide
(vii) Poly Phenylethene / Polystyrene
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Water soluble addition polymer
(i)
Solubility:
The addition polymer poly (ethenol) is
soluble in water because it can form many
strong hydrogen bonds with water molecule
Use:
Soluble laundry bags
(ii) Liquid detergent capsules.
Condensation Polymer
The linking together of two different monomers with different functional group or one monomers with
different functional group to form a large molecule with the elimination of a simple small molecule known
as condensation polymer.
The monomers usually have the same functional group on both ends of the same molecule
e.g. Ethane-1,2-diol, Benzene-1,4-dicarboxylic acid,Benzene-1,4-diacyl chloride.
The monomers also have the different functional groups on both ends of the same molecule
e.g. 2-hydroxypropanoic acid (lactic acid),4-aminobenzoic acid,1-hydroxybutanoyl chloride
Types of Monomer for Condensation Polymer
Monomer: Same functional group on both ends of the same molecule
Diol
Ethane-1,2-diol
1
OR
Benzene-1,4- diol
di-carboxylic acid
Hexanedioic acid OR
2
Benzene-1,4-
dicarboxylic acid
OR
4
di-acyl chloride
Hexane diacyl chloride
3
Benzene-1,4-diacyl
chloride
di-amine
Hexane-1,6-diamine OR
4
1,4- diaminobenzene
Monomer: Same functional group on both ends of the same molecule
Amine & Carboxylic
5 acid Aminoethanoic acid
together
4-aminobenzoic acid
6 Alcohol & acyl
chloride
together
1-hydroxybutanoyl chloride
7 Alcohol & Carboxylic
acid
together
2-hydroxypropanoic acid
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Type of Condensation Polymer Example
Polyesters PET / Terylene
Polyamides Nylon 6,6
Nylon 6
Kevlar
Ester An ester is formed by reacting carboxylic acid and alcohol in presence of an acid catalyst
OR, acyl chloride and alcohol without catalyst with eliminating water and HCl
Carboxylic Acid + Alcohol Acid catalyst Ester + water
Acyl chloride + Alcohol No catalyst Ester + HCl
Polyester
dicarboxylic Acid + diol Acid catalyst polyester + water
diacyl chloride + diol No catalyst polyester + HCl
Note:
Using the carboxylic acid to make the ester/polyester or amide/polyamide would only give an equilibrium mixture.
The more reactive acyl chloride goes to completion & does not need catalyst but does produce hazardous HCl fumes.
Amide An amide is formed by reacting either carboxylic acid with amine in presence of an acid catalyst
OR, acyl chloride with amine without catalyst
Carboxylic Acid + Amine ⇌ Acid catalyst Amide + H2O
Acyl chloride + Amine No catalyst Amide + HCl
Polyamide
dicarboxylic Acid + diamine ⇌ Acid catalyst poly(amide) + H2O
diacyl chloride + diamine No catalyst poly(amide) + HCl
Note:
Using the carboxylic acid to make the ester/polyester or amide/polyamide would only give an equilibrium mixture.
The more reactive acyl chloride goes to completion & does not need catalyst but does produce hazardous HCl fumes.
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Types of linkage in polymer
Polyester Ester linkage
Polyamide Amide linkage
OR
Monomers Functional group Linkage Bi-/ Polymer
Eliminating
product
dicarboxylic acid
Ester
+
H2O Polyester
diol
diacyl chloride HCl
+
diol
Amide
diamine + H2O
dicarboxylic acid Polyamide
diamine
+
diacyl chloride HCl
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POLYESTER: Polyethylene terephthalate (PET)/ Terylene
Monomers
Ethane-1,2-diol & Benzene-1,4-dicarboxylic acid
(terephthalic acid)
OR
Ethane-1,2-diol & Benzene-1,4-diacyl chloride
Mechanism Addition-elimination
Linkage Ester
Polymer Product Polyethylene terephthalate (PET) / Terylene
Eliminated product H2O OR HCl
Repeat unit
(i) Monomers: Ethane-1,2-diol & Benzene-1,4-diacyl chloride
Ethane-1,2-diol Benzene-1,4-dicarboxylic acid
Chemical Equation:
8
(ii) Monomers: Ethane-1,2-diol & Benzene-1,4-diacyl chloride
Ethane-1,2-diol Benzene-1,4-diacyl chloride
Chemical Equation:
9
POLYAMIDE: Nylon-6,6
Monomers
Hexane-1,6-diamine & Hexanedioic acid
OR
Hexane-1,6-diamine & Hexane diacyl chloride
Mechanism Addition-elimination
Linkage Amide
Polymer Product Nylon-6,6
Eliminated product H2O OR HCl
Repeat unit
Chemical reaction:
(i) Monomers: Hexane-1,6-diamine & Hexane diacyl chloride
Hexane-1,6-diamine Hexanedioic acid
Chemical Equation:
,
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(ii) Monomers: Hexane-1,6-diamine & Hexane diacyl chloride
Hexane-1,6-diamine Hexane diacyl chloride
Chemical Equation:
The 6, 6 of Nylon stands for number of carbons in each of the monomers (6 carbons) i.e. hexanedioic acid
and Hexane-1,6-diamine
POLYAMIDE: Nylon-6
Monomer: Caprolactum (cyclic amide)
Polymer:
The 6 stands for 6 carbons in the monomer (Caprolactum)
Note: The only example of nylon polymer that is not formed by condensation reaction because the monomer already
contains amide linkage. When heated in atmosphere of nitrogen then ring breaks open at the amide group.
The resulting chain is formed by joining together via existing amide linkage
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Uses of Nylon:
Used as fiber in clothing industry
used to make climbing ropes, tyre cords
Solid shape is used to make cogs and bearings in machines
POLYAMIDE: Kelvar
Monomers
Benzene-1,4-dicarboxylic acid & 1,4- diaminobenzene
OR
Benzene-1,4-diacyl chloride & 1,4- diaminobenzene
Mechanism Addition-elimination
Linkage Amide
Polymer Product Kelvar
Eliminated product H2O OR HCl
Repeat unit
Chemical reaction:
(i) Monomers are 1,4- diaminobenzene & Benzene-1,4-dicarboxylic acid
1,4- diaminobenzene Benzene-1,4-dicarboxylic acid
Chemical Equation:
n
+
12
(ii) (i) Monomers are 1,4- diaminobenzene & Benzene-1,4-diacyl chloride
1,4- diaminobenzene Benzene-1,4-diacyl chloride
Chemical Equation:
Properties:
low weight
high strength
less elastic and highly rigid
Uses:
To make strong material (5 times more than steel)
Used to prepare in bullet proof vests
Composites for boat construction
used as a reinforcement in car tyres, aircraft wings
Note:
It is also possible for polyamides to form from one monomer, if that monomer contains both the
functional
groups needed to react
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Write down the structure of monomer
SL Polymer monomer Eliminated
product
HCl
H2 O
H2 O
HCl
H2 O
HCl
H2 O
4
HCl
H2O
5
HCl
14
H2O
HCl
H2O
HCl
H2O
8
HCl
Uses of Polymers
‘Nylon’ and ‘Terylene’ are used to make clothes
Nylon is used for rope making
PVC is used as an electrical insulator, making pipes
Poly ethene is used to make plastic bags and electrical insulator
PROBLEMS ASSOCIATED WITH PLASTICS
Plastics are non-biodegradable – they cannot be decomposed by bacteria.
Therefore, much plastic waste will pollute the earth
Plastics produce toxic gas (such as hydrogen chloride) when burnt and this contributes to acid rain.
Plastics produce carbon dioxide when burnt – increases global warming.
Plastics produce poisonous carbon monoxide gas which prevents the oxygen to carry in the blood
Plastics that require CFC during production may contribute to depletion of ozone layer
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Green Polymers
Green Chemistry aims to reduce the demand for resources and energy, decrease waste and reduce
environmental pollution.
Principles of green polymer production include:
high resource effectiveness and high atom economy
clean production processes, which prevent waste and reduce greenhouse gas emissions
Use of renewable resources and renewable energy
Low carbon footprint.
Poly (ethylene furanoate) (PEF)
It is a green polymer made from bio-based monomers.
The monomers from which polymer made are furan-2,5-dicarboxylic acid and ethane-1,2-diol,
It’s form by condensation polymerization process.
The polymer is an ester so ester linkage present
The eliminating product is water
Chemical Reaction:
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Chemical reactivity of condensation polymers
The reactivity of condensation polymers can be explained by the presence of polar bonds which can attract
attacking species such as nucleophiles and acids
Polyesters and polyamides can be broken down by hydrolysis and are, therefore, biodegradable
Hydrolysis of Polyesters:
Polyesters can be hydrolyzed by acid and alkali. The acid hydrolysis is relatively slower than base hydrolysis
With HCl a polyester will be hydrolyzed and split up in to the original dicarboxylic acid and diol.
H+
–OCH2CH2OOC(C6H4)CO– HOOC (C6H4) COOH + HOCH2CH2OH
With NaOH an polyester will be hydrolyzed and split up into the diol and dicarboxylic acid salt.
NaOH
–OCH2CH2OOC(C6H4)CO– NaOOC (C6H4) COONa + HOCH2CH2OH
Hydrolysis of Polyamides:
Polyamides can be hydrolyzed by aqueous acids or alkalis.
With HCl an polyamide will be hydrolyzed and split up in to the dicarboxylic acid and diamine salt
H+
–NH (CH2)6NH-OC(CH2)4CO– HOOC(CH2)4COOH + H3N+ (CH2)6 +NH3
With NaOH an polyamide will be hydrolyzed and split up into the diamine and dicarboxylic acid salt
NaOH
–NH (CH2)6NH-OC (CH2)4CO– NaOOC (CH2)4COONa + H2N (CH2)6 NH2
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Intermolecular bonding between Polyesters chains:
Polyesters have permanent dipole bonding between the Cδ+ = Oδ- groups in the different chains
There are London forces between the chains.
Intermolecular bonding between Polyamides chains
Polyamides and proteins have hydrogen bonding between the lone pairs on oxygen in Cδ+ = Oδ-
groups and the H in the Nδ-–Hδ+ groups in the different chains.
There are also Permanent dipole-permanent dipole forces because the polar Cδ+ = Oδ- and C δ+–N δ-
and Nδ-–H δ+ bond
There are also London forces which are large because there are many electrons in the molecule
Polyamides will therefore have higher melting points than polyesters.
Properties of Addition/Condensation polymerization
……………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………………..…………………………………………………………………………………
Addition:
requires C=C/double bond
uses the same functional group
same general (empirical) formula as monomer different formula
no bi-product formed except polymer
Condensation:
no C=C/double bond is needed
needs two different functional groups
loss of small molecule is formed as bi-product with polymer
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