Polymerization

Wolmer’s Boys’ School
CAPE Unit 2 Chemistry
Module 1

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 Synthetic and Biological Polymers

Polymers: Macromolecules formed by the covalent

attachment of a set of small molecules (more than 50)
termed monomers.
Polymers are classified as:
(1) Man-made or synthetic polymers that are
synthesized in the laboratory;
(2) Biological polymer that are found in nature.

Synthetic polymers: nylon, poly-ethylene, poly-styrene

Biological polymers: DNA, proteins, carbohydrates

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 3

Types of Polymerisation
 Addition Polymerisation
 Condensation Polymerisation

 Polymers can be natural or synthetic.

 A natural addition polymers is rubber. Natural
condensation polymers are proteins and
carbohydrates.
 Synthetic addition polymers are PVC, PTFE,
polyethene.
 Synthetic condensation polymers are nylon 6.6 and
Terylene
 Methods for making polymers

Addition polymerization and condensation polymerization

•Addition polymerization: monomers react to form a

polymer without net loss of atoms. The monomers
used in addition polymerisation are alkenes or
derivatives of alkenes.
Most
•  common form: free radical chain reaction of
ethylenes

n monomers one polymer molecule 4

Example of addition polymers

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Examples of organic peroxides

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Free­Radical AdditionPolymerization of 
Ethylene
H2C CH2

200 °C organic

2000 atm peroxides

CH2 CH2 CH2 CH2 CH2 CH2 CH2

polyethylene
Free­Radical Polymerization of Propene
H2C CHCH3

CH CH CH CH CH CH CH
CH3 CH3 CH3 CH3 CH3 CH3 CH3

polypropylene
 A synopsis of the process
• Initiation
• An organic peroxide splits homolytically to produce 
two free radicals. 
• The free radical then attacks the monomer in this 
case, ethene.
• The pi bond in ethene is broken and one of the 
electron from the bond forms a bond with the radical. 
• The remaining pi electron is left on the next carbon 
atom and overall an ethene radical is obtained.   

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 A synopsis of the process
Propagation
•The ethene radical being unstable attacks 
another ethene monomer. This continues until 
termination reactions occur.
•Termination
•Termination occurs when two monomers 
react with each other.

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 ..
RO
..
 
•

H2C CHCH3
Mechanism
 ..
RO: Mechanism
H2C CHCH3
•
 ..
RO:

H2C  
CHCH3
•

H2C CHCH3
Mechanism
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3
•
 ..
RO:

H2C CHCH3

H2C  
CHCH3
•

H2C
Mechanism

CHCH3
 ..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•
  
..
RO: Mechanism
H2C CHCH3

H2C CHCH3

H2C CHCH3
•

H2C CHCH3
 Likewise...

•H2C=CHCl    polyvinyl chloride

•H2C=CHC6H5       polystyrene

•F2C=CF2        Teflon

  
Addition polymers (alkenes and other unsaturated compounds 
undergo addition polymerisation)
Molecular Structure
of Polymers
 Linear
 High Density Polyethylene (HDPE), PVC, Nylon,
Cotton
 Branched
 Low Density
Polyethylene (LDPE)
 Cross-linked
 Rubber
 Network
 Kevlar, Epoxy
Chain Length: 1000 - 2000
Low-Density Polyethylene
(LDPE)
LDPE
Conditions: 200 °C, 15
atmosphere. Melting point of
the polymer is about 105 °C
Uses: plastic bags, food
wraps, clothing items,
electrical insulation.
 Chain Length: 4,000 – 5,000

PVC – (polyvinyl chloride)

More Polar  Stronger Bonding

Uses of PVC
 PVC is more resistant than polyethylene.
 Blood bags, examination gloves, dialysis
equipment, pipes, window frames.
Chain Length: 10,000 –
High-Density Polyethylene
100,000

(HDPE)
HDPE
Conditions: 60 °C, 1 atmosphere,
Ziegler-Natta catalyst (triethyl
aluminium and TiCl4) Melting point
of the polymer is about 135 °C
Has higher tensile strength.
Uses: .tanks, crates, bowls,
bottles.
Chain Length: 2-6 million

Ultra-high-molecular-weight
polyethylene (UHMWPE)
Joint
Joint
Replacement
Replacement

Helmet

Gears
Natural Addition Polymer:
Rubber

 Sap:
 Sticky
 Viscous
 Gooey

 Goodyear
 Experiment
 Luck
 Profit ($0)
Vulcanization
Hardening of rubber using
sulfur.
The difficulty of disposing polyalkenes
1.Plastics are man-made, therefore no natural organism can
degrade them, i.e. non-biodegradable, thus dumping does not
solve the problem.

2.Plastics are also chemically inert, very unreactive, therefore

no none reaction can be used to dispose of them, however due
to new technologies, there are biodegradable plastics.

3.Very difficult to not use plastics as they have many uses

where glass would be either non-economical or unsafe. This
establishes our great need for polyalkenes.

4.Incineration is not the answer either, as this introduces

noxious fumes into the atmosphere which may do more harm
than good to the environment.
 Condensation polymerization

Condensation polymerization: the polymer grows from

monomers by splitting off a small molecule such as
water or carbon dioxide.

Example: formation of amide links and loss of water

Monomers

First unit of polymer + H2O

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In this process, with the addition of 2 or more monomers, there is
always the evolution of a small molecule usually water, HCl or
ammonia. Each monomer has AT LEAST two functional groups.
 33

Condensation
Polymerisation
 The product of condensation polymerisation
is dependent on the number of functional
end groups of the monomer. Those
monomers with only one functional group
will end a growing chain while those with
two or more ends will form linear polymers
or 3-D polymers with cross linkages
respectively.
 Condensation polymers are named based on
the linkages present in the polymer
 34

Condensation
Polymerisation
 Condensation polymers are bio-
degradable because the amide or ester
linkages between monomers can be
hydrolysed by acid, alkali or bacterial
enzymes.
 35

Polyester
 This polymer is produced in a condensation
reaction between diacids and dialcohols.
 Ester linkages form between monomers.

 Example Terylene formed from ethane-1,2-

diol and benzene-1,4-dicarboxylic acid.
 (Draw a representation of it in your books)

 Uses: clothing, track clothing, windbreakers

etc.
Chain Length: 4,000 – 8,000

Polyethylene Terephthalate (PET)

“Polyester”

Este
r
 Kevlar

Strong Network of Covalent

Bonds
And Polar Hydrogen Bonds
Rembember from GChem?

Nylon is a condensation polymer

made of the monomers adipic acid
and hexamethylene diamine.

O OH
O

OH
Qui ckT
i me™ and a
Photo - JPEG decompr essor
ar
e needed to see thi s pi ct ue.
r

Th
adipic acid
+
NH2
H2N

hexamethylene diamine

nylon
 Hydrogen bonds between chains

Supramolecular
Structure of
nylon

Intermolecular
hydrogen bonds
give nylon
enormous tensile
strength

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 40

Polyamides
 Polyamidesare made from monomers such as
di-amines and di-acids or di-acyl chlorides. An
monomer that has a carboxylic group on one
end and an amine group on the other end can
also be used.

 Nylon6.6 is a polyamide made from 1,6-

diaminohexane and hexane-1,6-dioic acid OR
hexanedioyl chloride. (DRAW IT IN YOUR BOOKS)

 Useof nylon: rope, carpets, parachute, combat

uniforms
Nylon
 Biopolymers

Nucleic acid polymers (DNA, RNA)

Amino acids polymers (Proteins)

Sugar polymers (Carbohydrates)

Genetic information for the cell: DNA

Structural strength and catalysis: Proteins

Energy source: Carbohydrates

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Polymers in Starch
Biology
DNA

Sugar Protein
s
 Proteins: amino acid monomers

The basic structure of an amino acid monomer

HO NH2
H
O R

The difference between amino acids is the R group

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 Proteins: condensation polymers

Formed by condensation polymerization of amino acids

Monomers: 20 essential amino acids

NH2 General structure of an amino acid
H R
CO2H R is the only variable group

Glycine (R = H) + Glycine First step toward poly(glycine)

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Representation of the
constitution of a protein

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Three D representation of the structure of a protein

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DNA
 Thymine (T)
The monomers:

Adenine (A)
Cytosine (C)

Guanine (G)

Phosphate-
Sugar (backbone) of
DNA
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Phosphate-
sugar
backbone
holds the DNA
macromolecule
together

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One strand
unwinds to
duplicate its
complement via a
polymerization of
the monomers
C, G, A and T

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Carbohydrates
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 Cotton

Long Strands of Cellulose

+ Hydrogen Bonds

Cellulose is the most common organic material on earth!

It is also a primary constituent of wood and paper.
Comparison of properties of a monomer and its polymer (using
glucose and starch)

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Endless Possibilities

 New
Function
al Groups

 Different
Polymer
Backbones
Conclusions:
 Polymers make up all sorts of materials that
are all around us!
 They can have a huge range or material
properties based on their:
 Functional Groups
 Structure
 Backbone
 Keep thinking about how chemical
interactions on the nano-scale correspond
to material properties on the macro-scale
Links
 http://en.wikipedia.org/wiki/Plastic_recycling
 http://en.wikipedia.org/wiki/Alkane
 http://en.wikipedia.org/wiki/Higher_alkanes
 http://en.wikipedia.org/wiki/Ultra-high-molecular-weight_polyethylene
 http://en.wikipedia.org/wiki/Polycondensation
 http://www.chemistryland.com/ElementarySchool/BuildingBlocks/BuildingOr
ganic.htm
 http://www.ndt-
ed.org/EducationResources/CommunityCollege/Materials/Structure/polymer.
htm
 http://www.bbc.co.uk/schools/gcsebitesize/science/21c/materials/molecstru
ctpropertiesrev3.shtml
 http://en.wikipedia.org/wiki/Van_der_Waals_force
 http://en.wikipedia.org/wiki/Vulcanization
 http://www.scribd.com/doc/26766586/08-Polymers-Why-is-Rubber-Elastic
 http://www.ndt-
ed.org/EducationResources/CommunityCollege/Materials/Structure/polymer.
htm