UNIT III Polymer Chemistry
Basic Concepts
K. Rajendra Kumar
Department of Chemistry
VIT Chennai campus
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INTRODUCTION
First naturally known polymers - Gum acacia, rubber
A word polymer is a combination of two Greek words,
“Poly” means “many” and “mer” means “units”.
A polymer is a large molecule of which is formed by
repeated linking of the small molecules called
“monomers”.
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A Brief History of Modern Polymer Science - Some Highlights
(1800 A.D. to 2011 A.D.)
Acetylation of Cellulose – 1830s
Vulcanization of Natural Rubber – 1830s
Viscose Rayon Process – 1860s
Phenol-Formaldehye Resin (Thermosetting Polymer) – 1907 Leo Baekland
Free radical polymerization ~1910 to 1930
Concept of the existence of giant molecules or macromolecules
-Hermann Staudinger 1918
Free radical polymerization kinetics elucidated in 1930s
First systematic synthesis of polyesters and polyamides by the
condensation of between small molecules (adipic acid and ethylene glycol
or ethlyene diamine) – 1930s by Wallace Carothers.
Early 1930s the existence of macromolecules accepted by Scientists
who thought that they were colloids earlier. By 1940s rapid development
in the synthesis and mechanism of polymerization.
By the beginning of 1950s it was well accepted that macromolecules
could be synthesized by either the chain growth (largely free radical)
or the step growth (largely organic transformations).
DEGREE OF POLYMERIZATION
• The number of repeating units in the chains of which
a polymer is made up is called degree of a
polymerization (n).
• Polymers with high degree of polymerization are
called the “High Polymer”, and those with low
degree of polymerization are called “Oligomers”.
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CLASSIFICATION OF POLYMERS
Based on repeating units
• Homopolymers – same type of repeating units
through out the polymer chain
• Copolymers – More than one type of monomeric
repeating units in the polymer chain
Based on architecture
• Polymers can be linear, branched or cross-linked. The
monomer may be arranged in the chain at random or
regularly.
Based on source
• Natural Polymers - Cellulose, Protein,
Polynucleotides,Enzymes, Polysaccharides etc.
• Synthetic Polymers – All manmade polymers 5
Based on molecular forces
1. Elastomers
Buna-S, Buna-N, neoprene
2. Fibers
Polyesters, Polyamides.
3. Thermoplastic polymers
Polythene, Polystyrene, PVC.
4. Thermosetting polymers
Bakelite, urea-formaldelyde resins
Order of strength
Thermosetting > Fibres > Thermoplastics > Elastomers
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Based on mode of polymerization
1 Addition polymers
formed by the repeated addition of monomer molecules possessing
double or triple bonds
n(CH2=CH2) -(CH2 -CH2 )n-
Ethylene polyethylene
2 Condensation polymers
formed by repeated condensation reaction between two different bi-
functional or tri-functional monomeric units.
eg. terylene (dacron), nylon 6, 6, nylon 6.
n(H2N(CH2)6 NH2) + n(HOOC(CH2)4COOH)
[-NH(CH2)6NHCO(CH2)4CO-]n + nH2O
(Nylon 6:6)
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3. Copolymerisation:- is a polymerization reaction in which a mixture
of more than one monomeric species is allowed to polymerize and form
a copolymer. For example, a mixture of 1, 3 – butadiene and styrene can
form a copolymer.
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POLYMERIZATION METHODS
• Widely used are
Addition/chain polymerization
Condensation/step-growth polymerization
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ADDITION/CHAIN POLYMERIZATION
*Monomers should have multiple bonds (double/triple)
*Monomers are just added (called ‘zipping’)
*No by-products are formed (small molecules like
water, HCl, ammonia etc.,)
*Polymer formed is the exact multiple of molecular
weight of the monomer
* Based on the initiating species (radical/cation/anion)
three types of addition/chain polymerization are
Free radical polymerization
Cationic polymerization
Anionic polymerization Living polymerization techniques
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General Mechanism of Chain Polymerizations
Addition polymerization proceeds by the initial
formation of some reactive species such as free
radicals or ions followed by its addition to the
monomers.
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Mechanism of Free radical polymerization
Monomers : Alkenes or dienes and their derivatives
Initiators: Free radical generating initiators(catalyst) like benzoyl
peroxide, acetyl peroxide, t-butyl peroxide, etc.
Steps involved
a) Chain initiation - addition of free radical formed by the peroxide to
the ethene double bond ,thereby forming a larger radical.
b) Chain propagation - repetition of this sequence with new and bigger
radicals.
c) Chain termination - the product radical thus formed reacts
with another radical to form the polymerized product.
Examples Polystyrene, Polymethyl methacrlate (PMMA)
Polytetrafluroethene (PTFE/Teflon), Polyacrylonitrile (PAN),
Low Density Polyethylene (LDPE) 12
Initiation
In chain initiation step, a free radical is first generated
as a result of physical or chemical effect, which is
responsible for the further continuation of the chain
polymerization
Half-life of isobutyronitrile radical : 1.3 h at 80℃. 13
Initiation and Propagation
The primary free radical react with the double bond of
an unexcited monomer molecule and adds to it
forming a new radical capable of further interaction
with the initial monomers.
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Termination
The most common termination processes are radical combination
and disproportionation.
These reactions are illustrated by the following equations.
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Plastics production statistics 2004
source : American plastics council
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Shape of polymeric molecules
• C-C bond angle is 109o, but there is rotation
freedom.
This means that the molecules are not straight, and will
form random 3-D messes, like a plate of spaghetti.
Crystalline or Amorphous?
Symmetry or non symmetry?
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TACTICITY
It’s all about symmetry!!
Q: If random coils were to “uncoil” into a straight chain, how well can you
predict the location of subsequent atoms?
A : The more predictable, the higher the crystallinity
For example, consider polyethylene
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Methyl substitutions to one side of backbone
high degree of equilibrium crystallinity
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Methyl substitutions on alternate sides of backbone
No backbone irregularity
high degree of equilibrium
crystallinity
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ATACTIC POLYPROPYLENE
To get significant tacticity, a highly structured active site which can “pre-orient”
monomer with respect to the growing chain and hence add in a stereospecific way is
much needed. Zeigler Natta catalyst !!
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