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Polymers
• Polymers are macromolecules formed by repeated joining of many
small molecules.
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Chemistry in Action (Polymers)
Natural Polymers
Amino acids and protein
Introduction
Amino acid are bifunctional compounds containing both the amino (-NH2) and
carboxylic (-COOH) groups.
NH2 COOH
COOH
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Chemistry in Action (Polymers)
They are optical isomers, but optical inactive, since they are racemic mixture.
Laboratory synthesized amino acids are ONLY optically inactive because of
the formation of race mixture.
In fact, in the solid state and in solution, amino cids exist as internal ionic
salts, called Zwitterions.
So,
Amino acids are high melting point solids.
e.g. Glycine melts at 235℃
They are very soluble in water, but they only dissolove slightly in organic
solvents.
They have a very large dipole moment.
+ OH− + OH−
H3N – CH – COOH H3N – CH – COO− H2N – CH – COO−
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| H+ | H+ |
R R R
Chemistry in Action (Polymers)
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Chemistry in Action (Polymers)
Dil. NaOH(aq) H
NH2 CCOO-Na+
R
HO
SOCl2 or PCl5
NH2 C-C-Cl
Showing acidic R
Properties H
Fusing with soda lime NH2-C-H
R
HO
CH3OH/H+ +
H NH3 C-C-OCH3
NH2 CCOOH R
R
H
Dil HCl - +
Cl NH3 CCOOH
Showing basic
Properties R
OHH
CH3COCl
CH3-C-N-C-COOH
R
The (-NH2) group of one amino acid can react with the (-COOH) group of
another to form an amide.
The resultion molecule is a dimmer containing two amino acid units which is
describes as a dipeptide.
In the process, the two amino acid molecules are joined by the condensation
reaction. A water molecule is eliminated.
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Chemistry in Action (Polymers)
Polypeptide
Amino acids undergo condensation polymerization to form long-chain
polyamide molecules.
dipeptide
Further
reaction
of each
end
Polypeptide/protein
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Chemistry in Action (Polymers)
Structure of proteins
Protein structure is describe at 4 levels: 1∘, 2∘, 3∘ & quaternary.
Being polyamides, both proteins and nylon can be hydrolysed and are thus
broken down to their constituent amino acids.
For example,
Polypeptide
Dipeptide
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Chemistry in Action (Polymers)
Amino acids
Carbohydrates
Monosaccharide, disaccharide and polysaccharide
The simplest carbohydrates are the sugars. (glucose, fructose and ribose)
Monosaccharides
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Chemistry in Action (Polymers)
Each monosaccharides molecule contains one carbonyl group. All the other
carbon atoms are bonded to hydroxyl groups. There are aldose and ketose,
for which the carbonyl group is and is NOT terminal respectively.
aldehyde
ketone
0.02%
36% 64%
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Chemistry in Action (Polymers)
Disaccharides
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Chemistry in Action (Polymers)
Polysaccharides
Polysaccharides are polymers of monosaccharides
General formula: (C6H10O5)n where n is a large number (up to thousands)
Examples of polysaccharides: starch and cellulose
Starch is commonly found in rice, bread and potatoes
Cellulose is found in fruits, vegetables, cotton and wood
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Chemistry in Action (Polymers)
Cellulose
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Chemistry in Action (Polymers)
Nucleic acid molecules are long polymers of small monomeric units called
nucleotides.
The monomers of nucleic acids, called nucleotides, are formed from the
following units:
1. A phosphate unit
2. A five carbon sugar
3. A nitrogen – containing organic base.
Two kinds of nucleic acids: deoxyribonucleic acid (DNA) and ribonucleic acid
(RNA)
Deoxyribos
Ribose e
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Chemistry in Action (Polymers)
(in DNA)
(in RNA)
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Chemistry in Action (Polymers)
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Chemistry in Action (Polymers)
DNA replication
The original DNA double helix partially
unwinds, and new nucleotides line up on
each strand in a complementary manner.
Hydrogen bonds help align the new
nucleotides with the original DNA chain.
When the new nucleotides are joined by
condensation reactions, two identical double
helix DNA molecules result.
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Chemistry in Action (Polymers)
Synthetic Polymers
Addition Polymers
Formation and Uses of Addition Polymer
Addition polymerization is a chemical process in which monomer molecules
are joined together to form a polymer without elimination of small molecules.
The resulting polymer will therefore have the same percentage composition
as the reactant monomers.
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Chemistry in Action (Polymers)
Polyethene is a thermoplastic
It softens at a high temperature
Uses of polyethene
Insulate telephone line
Its unique electrical properties were essential during the development of
radar.
Plastic bags
It used in supermarket for packing various food product.
milk bottles and water buckets
Hard and rigid, not poisonous
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Chemistry in Action (Polymers)
Chain propagation
2. Polypropene (PP)
With the use of Ziegler-Natta catalyst, propene can be polymerized to
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Chemistry in Action (Polymers)
polypropene
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Chemistry in Action (Polymers)
3. Polystyrene (PS)
Styrene is made from the reaction of benzene with ethane, followed by
dehydrogenation.
Mechanism:
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Chemistry in Action (Polymers)
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Chemistry in Action (Polymers)
(a) (b)
Presence of the polar C – Cl bond is considerable
dipole-dipole interactions exist between the polymer chains makes PVC a
fairly strong material
The large size of Cl atom means the chains cannot easily be moved over one
another. This result in the polymer being rigid and brittle.
PVC is hard and brittle and used to make pipes and bottles
Products made
of PVC without
plasticizers
When plasticizers are added, the effectiveness of the dipole- dipole
interactions is reduced. PVC becomes more flexible
• Used to make shower curtains, raincoats and artificial leather
• Used as the insulating coating of electrical wires
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Chemistry in Action (Polymers)
Products made
of PVC with
plasticizers
Despite its extensive uses, one problem with the use of PVC is its disposal.
PVC is non-biodegradable, normally not disposed of by land-filling.
Incineration of PVC produces HCl (g)
This HCl (g) produced is usually absorbed by the wet scrubber filled with an
alkali such as Na2CO3 (aq).
5. Polytetrafluoroethene (PTFE)
PTFE is produced through addition polymerization of the tetrafluoroethene
monomers under high pressure and in the presence of a catalyst
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Chemistry in Action (Polymers)
C—F bonds are exceptionally strong & resistant to heat and chemicals
PTFE has a relatively high melting point and is chemically inert
Its non-stick properties make it an ideal material for the coating of frying pans
⇒Since fluorine is highly electronegative atom an evenly distributed layer of
negative charge is developed on the surface of PTFE
⇒ Layers of negative F atoms repel almost all other materials
⇒ Thus preventing them from adhering to PTFE
⇒ PTFE has very slippery surface
Whatever the technique, there is still the chance of Teflon peeling off from
cooking ware after extended use, because
⇒Teflon decompose at high temperature
⇒Its coefficient of expsion is different from that of the material of the cooking
surface
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Chemistry in Action (Polymers)
PMMA is a dense, transparent and tough solid makes it a good material for
making safety goggles, advertising sign boards and vehicle light protectors
However, it has poor scrtching resistance and can be dissolved by a number
of organic solvents.
Condensation Polymers
Formation and Uses of Condensation Polymer
Condensation polymerization is a chemical process in which monomer
molecules are joined together to form a polymer with elimination of small
molecules such as water, ammonia and hydrogen chloride
1. Polyamide
1. Nylon
Nylon 6,6
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Chemistry in Action (Polymers)
faster
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Chemistry in Action (Polymers)
3. Kevlar
Aramid is a synthetic poly amide
Aliphatic hydrocarbon unit within the polmer chain has been replaced by an
aromatic unit in Aramid
• Kevlar is an aromatic polyamide
• The structure of Kevlar is similar to nylon-6,6
• The two monomers of Kevlar are benzene-1,4-dicarboxylic acid and
1,4-diaminobenzene
Both monomers are bifunctional
In Kevlar, the starting material was modified to create straighter chains in the
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Chemistry in Action (Polymers)
In Kevlar the aliphatic hydrocarbon chain parts of the poly amide are replaced
by benzene rings. These parts of the polymer chain make the chains inflexible
due to delocalized bonding.
Some of this delocalization extends beyond the benzene rings and onto part
of the amide link resulting in long, rigid molecules that do not easily flex or
twist.
All the C = O and – N – H groups in the polymer chains are on opposite sides.
This makes the chains highly symmetrical. The regular structure of the
polymer chains allows them to interlock with each other.
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Chemistry in Action (Polymers)
Applications:
(a) Kevlar is an unusual polymer with fire resistant properties and also
great strength. It is found in the crash helmets of Formula I racing
drivers as well as in the suits of racing motorcyclists.
(b) The hull of this offshore racing craft is also reinforced with Kevlar.
(c) Kevlar is used in making bullet proof vests. A more recent innovation is
to use carbonanotubes to make fibres for these bullet proof vests.
These new bullet proof vests can be made 30 % lighter, but 1.5 times
more bullet resistant than conventional Kevlar vests.
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Chemistry in Action (Polymers)
(b)
(a)
(c)
2. Dacron
Formed by repeated condensation reactions of benzene-1,4-dicarboxylic acid
(also called terephthalic acid) and ethane-1,2-diol (also called ethylene glycol)
in the presence of a catalyst and at a low pressure and moderate temperature
(about 250°C)
Due to polarization of the carbonyl groups C=O, Dacron chains are cross-
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Chemistry in Action (Polymers)
⋅ ⋅ ⋅ ⋅
⋅⋅ ⋅⋅ ⋅⋅ ⋅⋅
⋅⋅ ⋅⋅ ⋅⋅ ⋅⋅
⋅ ⋅ ⋅ ⋅
Properties of Dacron:
High tensile strength
High resistance to stretching
Low absorption of moisture
Garments made of Dacron:
are tough
can resist wrinkling
can be washed and dried easily and quickly
Excellent for making trousers and skirts, sheets and boat sails
Can be used alone or blended with cotton to make it absorb sweat better
3. Urea-methanal
Produced by the condensation polymerization of urea and methanal under
heat and pressure
When an urea molecule joins up with a methanal molecule, water molecule is
eliminated
In the presence of excess methanal, further condensation reactions between
the polymer chains and methanal occur.Cross-linkages between the polymer
chains are formed. A rigid structure of urea-methanal is produced
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Chemistry in Action (Polymers)
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Chemistry in Action (Polymers)
• Polymer chains containing carbon and hydrogen atoms only are held
together by weak van der Waals’ force
• slow melting points
• low mechanical strength
• If polymer chains are held together by stronger van der Waals’ forces
or hydrogen bonds, the mechanical strength of the polymers would be
stronger
• If cross-linkages are present between polymer chains, the polymers
would be mechanically stronger, more elastic or more rigid ,depending
on the extent of cross- linkages in the polymer
blow-molded objects: bottles for milk, soft drinks, shampoos, bleaches and so
on
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Chemistry in Action (Polymers)
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Chemistry in Action (Polymers)
random manner
• When nylon is spun into fibres and is drawn
• the crystalline regions are aligned
• leads to an increase in the tensile strength
Non-aligned
crystalline region
Aligned
crystalline
region
In the stretched or drawn nylon, the polymer chains line up and are parallel to
each other. The amide groups on adjacent chains form strong hydrogen
bonds with each other
These hydrogen bonds hold the adjacent chains together making nylon thread
strong
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Chemistry in Action (Polymers)
Vulcanization of Polymers
Natural rubber is a polymer of the monomer
2-methylbuta-1,3-diene (isoprene)
2-Methylbuta-1,3-diene
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Chemistry in Action (Polymers)
This makes the rubber harder and reduces its susceptibility to oxidation or
other chemical attrack.
• When vulcanized rubber gets hot, the polymer chains cannot slip
across one another since they are still held together by short chains of
sulphur atoms
• That is why vulcanized rubber does not melt when heated and does not
become brittle when cooled
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Chemistry in Action (Polymers)
The extent of the cross-linkages formed between the polymer chains affects
the properties of vulcanized rubber
• If the rubber has few cross-linkages, the rubber is softer, more flexible
and more elastic
• If the rubber has many cross-linkages, it is stiffer, less flexible and less
elastic
• Car tyres are made of vulcanized rubber
• Because of the presence of cross-linkages among the polymer chains,
the rubber does not melt when it gets hot
• That is the reason why car tyres do not melt when drivers drive really
fast
Degradable Plastics
• Natural polymers (e.g. wood and paper) are
biodegradable Micro-organisms in water and in the
soil use them as food
• Synthetic polymers (e.g. plastics) are non-
biodegradable can remain in the environment for a
very long time
• Nowadays, plastic waste constitutes about 7 % of
household waste
• In Hong Kong, plastic waste is buried in landfill sites
it remains unchanged for decades
more and more landfill sites have to be found
Uses of plastics in Hong Kong (an approximation)
(a) Hong Kong is a highly densely populated city
(b) The volume of domestic waste generated daily is very great.
(c) Plastic waste contributes to the main bulk of our domestic waste.
(d) Few sites are left to be used for landfill
(e) The building / operation cost of incineration plants is high and recycling
of plastics also involves very tedious procedures.
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Chemistry in Action (Polymers)
1. Biopolymers
• Polymers made by living micro-organisms (e.g. paracoccus, bacillus
and spirullum)
• e.g. The biopolymer poly(3-hydroxybutanoic acid) (PHB) is made by
certain bacteria from glucose
• When PHB is disposed, the micro-organisms found in the soil and
natural water sources are able to break it down within 9 months
• However, PHB is 15 times more expensive than polyethene
(c) Spirullum
2. Photodegradable Plastics
• Photodegradable plastics have light-sensitive functional groups (e.g.
carbonyl groups) incorporated into their polymer chains
• These groups will absorb sunlight use the energy to break the chemical
bonds in the polymer to form small fragments
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Chemistry in Action (Polymers)
END
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