Ahsanullah University of Science and Technology

Department of Textile Engineering

Coures Title: Textile Technology

Polymer and Polymerisation

Mohammad Tajul Islam

tajul.dtt@aust.edu

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Hermann Staudinger
 Prior to the early1920's, chemists doubted the existence of
molecules having molecular weights greater than a few
thousand.

 This limiting view was challenged in 1925

by Hermann Staudinger, a German chemist
with experience in studying natural
compounds such as rubber and cellulose.

 For his contributions to chemistry, Staudinger received the 1953

Nobel Prize.

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Macromolecules
 In contrast to the prevailing rationalization of these substances as
aggregates of small molecules, Staudinger proposed they were
made up of macromolecules composed of 10,000 or more atoms.

 He formulated a polymeric structure for rubber,

based on a repeating isoprene unit (referred to
as a monomer) (1925).

 Recognition that natural polymeric macromolecules make up many

important natural materials was followed by the creation of
synthetic analogs having a variety of properties (1931-1935 Nylon).

 Indeed, applications of these materials as fibers, flexible films,

adhesives, resistant paints and tough but light solids have
transformed modern society.

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Polymers and Polymerization
 A polymer (from Greek po΄li-s/ much, many and ΄meros/ part) is a
large molecule (macromolecule) composed of repeating
structural units typically connected by covalent chemical bonds.
 Polymerization is the process of combining many small
molecules known as monomers into a covalently bonded chain.

 There are many polymerization reactions,but all polymerizations

have one thing in common: they all start with small molecules
(monomers), and join them into big giant molecules.
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Monomers
 Examples of monomer molecues

 The highlighted areas show the side groups on these monomer

molecules. These groups give the polymer chain some of its
properties.
 The double bond, however, is the vital feature that allows these
monomers to form the long polymer chains.

 What is the feature found in each of these monomers?

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Monomers, Structural unit & Repeat unit
 The distinct piece of monomer that is incorporated into the
polymer is known as a structural unit

One Structural unit

One Monomer
One Repeating unit

Two Monomers

Two Structural units

One Repeating unit

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Monomers, Structural unit & Repeat unit
 In polymer chemistry, a structural unit is a building block of a
polymer chain, and related to the repeat unit. It is the result of a
monomer which has been polymerized into a long chain.
 When different monomer are polymerized, a copolymer is formed.

 Take polyethylene terephthalate: -[CH2-CH2-O-CO-Ph-CO-O]n-

 The monomers which could be used to create this polymer are

ethylene glycol and terephthalic acid:
HO-CH2-CH2-OH and HOOC-Ph-COOH

 In the polymer, there are two structural units, which are:

-O-CH2-CH2-O- and -CO-Ph-CO-
 The repeat unit is: -CH2-CH2-O-CO-Ph-CO-O-

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Repeat unit
 The repeating structural unit of most simple polymers not only
reflects the monomer(s) from which the polymers are
constructed, but also provides a concise means for drawing
structures to represent these macromolecules.
 Here ethylene (ethene) is the monomer, and one of the corresponding linear
polymers is called high-density polyethylene (HDPE). HDPE is composed of
macromolecules in which n ranges from 10,000 to 100,000
(molecular weight: 2 x 105 to 3 x 106 ).

 This polymer is called polyethylene rather than polymethylene, (-CH2-)n, because

ethylene is a stable compound (methylene is not), and it also serves as the
synthetic precursor of the polymer.
 The two open bonds remaining at the ends of the long chain of carbons (colored
magenta) are normally not specified, because the atoms or groups found there
depend on the chemical process used for polymerization.

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Homo & Copolymers
Macromolecules are composed of one or more than one
monomeric repeating unit:
 Homopolymers where only one monomer is used (1)
 Alternating copolymers with regular alternating A and B units (2)
 Random copolymers, in which the sequence of monomer residues (structural
units) doesnʼt follow any statistical rule (3)
 Block copolymers comprise two or more
homopolymer subunits linked by
covalent bonds (4)
 Linear copolymers consist of a single main
chain
 Branched copolymers consist of a single
main chain with one or more polymeric
side chains
 Graft copolymers are a special type of
branched copolymer in which the side chains
are structurally distinct from the main chain (5)

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Degree of polymerization
 The degree of polymerization, or DP, is the number of repeat
units in a polymer chain.
 The degree of polymerization is a measure of the molecular
weight (MW). For most industrial purposes, lengths in the
thousands or tens of thousands are desired.
 For a homopolymer, the degree of polymerization may be
calculated as shown below

Polymerization Degree Number of repeating units

(DP) in the polymer chain

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Degree of polymerization
 Polymers with identical composition but different total molecular
weights may exhibit different physical properties.
 In general, increasing degree of polymerization correlates with
higher melting temperature and higher mechanical strength.

 Relationship between degree of polymerization and melting temperature for polyethylene

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Average Molecular Weight
 Unlike simpler pure compounds, most polymers are composed of
molecules of different length (different DP).
 Because of this, polymer molecular weights are usually given as
averages. Two experimentally determined values are common:

 Mn, the number average molecular weight, is calculated from the

number fraction distribution of different sized molecules in a
sample;

 Mw, the weight average molecular weight, is calculated from the

weight fraction distribution of different sized molecules.

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Polymerisation: classification systems
 There are many forms of polymerization and different systems
exist to categorize them.
Most important classification systems are:

1) the Addition-Condensation system

2) the Chain Growth - Step Growth system

 Each has its own criteria, and the distinctions made by one
system are not always going to be the same as the distinctions
made by the other.
So don't try to reconcile the two systems.
Just know that polymerizations can be step growth or chain
growth, and they can be condensation or addition.

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The Addition-Condensation System
 In addition polymerization the entire monomer molecule becomes
part of the polymer

n CH2 = CH2 -[CH2 - CH2]n -

 In condensation polymerization, part of the monomer molecule is

kicked out when the monomer becomes part of the polymer. The
part that gets kicked out is usually a small molecule like water,
HCl, ...

n HOOC-(CH2)4-COOH + n H2N-(CH2)6-NH2 -[-OC-(CH2)4-CO-NH-(CH2)6-NH-]n- +2nH2O

 Because there is less mass in the polymer than in the original monomers, we
say that the polymer is condensed with regard to the monomers. The
byproduct, whether it's HCl gas, water, or whatnot, is called a condensate.
 Condensation polymerizations give off byproducts. Addition
polymerizations don't.
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The Chain Growth - Step Growth system
 Chain growth polymerization is a polymerisation technique where
unsaturated monomer molecules add on to a growing polymer
chain one at a time. Two growing chains can't join together: only
monomers may react with growing chains.

n M (monomer) (-M-)n (polymer)

where n is the degree of polymerization

 Step growth polymerisation is a stepwise reaction between

functional groups of monomers. In a step-growth reaction, the
growing chains may react with each other to form even longer
chains. This applies to chains of all lengths.
Thus, a monomer or dimer may react in just the same way as a
chain hundreds of monomer units long

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Step growth polymerisation
 Most step growth polymers are also classified as condensation
polymers, when linking of low molecular compounds
simultaneously split off byproducts, e.g. small molecules as
water, alcohols etc.

n M1 + n M2 (Repeat unit)n + By-products

 But not all step growth release condensates (like polyurethanes

formed from isocyanate and alcohol bifunctional monomers).
n M1 + n M2 (M1-M2)n

 Polymers that do not split off byproducts during polymerisation

are also called polyaddition polymers.


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Step growth polymerisation
 Bi-functional or multifunctional monomers react to form first dimers,
then trimers, longer oligomers and eventually long chain polymers.

M+M M-M (Dimer)

M-M + M M-M-M (Trimer)
M-M-M + M M-M-M-M (Tetramer)
M-M + M-M M-M-M-M (Tetramer)
-------- + -------- -------------------- (Polymer)

(Single white dots represent monomers and

black chains represent oligomers and polymers)

 In theory the polymerisation will continue to result in a single

macromolecule, but in practice, the chain length is controlled
stopping the growth with appropriate chemicals.
 Short polymers (oligomers) are also produced.

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Step growth polymerisation
 The prerequisite for reactions of this type is the presence in the
molecule (monomer) of reactive groups with functional
properties.
 A multifunctional monomer is a molecule that has more than one
potential reactive site by which it can form intermolecular
chemical bonds.
 The functionality of a monomer is the number of reactive sites.

 A functionality of 2 will yield a linear polymer.

 A functionality of 3 will yield a branched polymer.

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Step growth polymerisation
 Let's take a look at the step growth polymerization of two monomers, terephthoyl
chloride and ethylene glycol, to make a polyester called poly(ethylene
terephthalate). The first thing that happens is that the two monomers will react to
form a dimer

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Step growth polymerisation
 Now at this point in a chain growth system, only one thing could happen: a third
monomer would add to the dimer to form a trimer, then a fourth to form a
tetramer, and so on. But in step growth polymerization, that dimer can do a lot of
different things. It can of course react with one of the monomers to form a trimer:

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Step growth polymerisation
 But it can do other things, too. It may react with another dimer to form a tetramer:

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Step growth polymerisation
 Or it may even react with a trimer to form a pentamer.

 Tetramers and pentamers can react to form even bigger oligomers. And so they
grow and grow until eventually the oligomers are big enough to be called
polymers.

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Chain growth polymerisation
 In a chain growth polymerization, monomers become part of the
polymer one at a time.

 Unlike condensation polymerization :

- high molecular weight polymer is formed even at low

conversion

- no small molecules, such as H2O, are eliminated

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Chain growth polymerisation
 Example of Chain growth polymerization: in the anionic
polymerisation of styrene, only styrene monomes can react with
the growing chain.

 The growing chains wonʼt react with each other.

they reject

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