Introduction to Polymer

Science and Engineering

Zenamarkos B. (PhD)
Ayalneh A. (BSc)

Chemical Engineering Program

Faculty of Chemical and Food Engineering
Bahir Dar Institute of Technology (BiT)
Bahir Dar University
March, 2022
 Introduction Polymer Science and Engineering

General Information:
Academic year: 2021/2022
Study Points: 4 CP
Language: English
Duration: 64 hrs

Aim: Levelling of students bases in:

 polymer physico-chemistry
 polymer processing

Course materials:
Text books, PPTs
Articles and literature
2
 Contents
Chapter 1: Polymer Synthesis
 Introduction to Polymers
 Polymerization Processes
 kinetic schemes

3
 Contents
Chapter 2: Determination of Molecular Weight &
Distribution (MWD)
 Determination of Molecular weight
 Determination of molecular weight distribution
Relative
fraction

Molecular weight
4
 Contents
Chapter 3: Characterization of Polymers
 Classification of polymer
 Chain Structure and Configuration
 Polymer Morphologies
 Methods for determining the percent of crystallinity

Semi-crystalline Amorphous
5
 Contents
Chapter 4: Plastic Processing Technologies
 Introduction to plastic engineering
 Plastic processing
 Extrusion
 Injection Molding

6
Text books

7
Course Goal

Polymerization

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POLYMER
SYNTHESIS

9
 Introduction
֍ Polymer: a macromolecule, composed of many repeated subunits.

Poly- => "many" + -mer => "parts" or “segment"

Polypropylene

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 Introduction
Monomer (‘Repeating Unit’):
 a molecule of any of a class of compounds, mostly organic, that can
react with itself or other molecules to form very large molecules,
or polymers.

 The essential feature of a monomer is polyfunctionality, the capacity

to form chemical bonds to at least two other monomer molecules.
 Bifunctional monomers can form only linear, chainlike polymers,
but monomers of higher functionality yield cross-linked, network
polymeric products.

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 Introduction
 Polymerization:

 any process in which small molecules (monomers) combine chemically

to produce a very large chainlike or network molecule, called a polymer.

 The monomer molecules may be all alike, or they may represent two or
more different compounds.

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 Introduction
 Degree of polymerization :number of repeating units in a polymer.

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Polymerization Processes
 Polymerization Processes

based on the compositional

 Addition Polymerization differences between the
polymer and the monomer(s)
from which the polymers were
 Condensation Polymerization synthesized.

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 Polymerization Processes
Addition Polymers:
 formed from monomers with out the loss of a small molecule.
 mostly, the repeating unit of an addition polymer has the same
composition as the monomer.
 monomers contain carbon-carbon double bond => Vinyl monomers.

(diols) (diisocyanates)

(polyurethanes)

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 Polymerization Processes
Addition Polymers:
 The distinguishing characteristic of addition polymerization is that
polymer growth takes place by monomer reacting only with the
reactive center.
 Monomer does not react with monomer and the different-sized species
such as dimer, trimer, tetramer, and n-mer do not react with each
other.

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 Polymerization Processes
Addition Polymers:
 Each monomer molecule that adds to a reactive center regenerates the
reactive center.
 Polymer growth proceeds by the successive additions of hundreds or
thousands or more monomer molecules.
 The growth of the polymer chain ceases when the reactive center is destroyed
by one or more of a number of possible termination reactions.
 The only change that occurs with conversion (i.e., reaction time) is the
continuous increase in the number of polymer molecules.
 High molecular-weight polymer molecules are obtained at all conversion
levels (e.g., 0.1, 1, 10, 40, 90%).

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 Polymerization Processes
Addition Polymers:

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 Polymerization Processes
Condensation Polymers:

 formed from polyfunctional monomers by various condensation

reactions with the elimination of some small molecules such as
water.

(diamines) (diacids)

(polyamides)

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 Polymerization Processes
Condensation Polymers:

(diols) (diacids)

(phosgene)

(dihydroxy)

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 Polymerization Processes
Condensation Polymers:

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 Polymerization Processes
Condensation Polymers:
 The characteristics of step polymerization that distinguishes it from
chain-growth polymerization is that reaction occurs between any of the
different-sized species present in the reaction system.
 High molecular-weight polymer is obtained only near the very end of
the reaction (>98% conversion).

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 Polymerization Processes
Condensation Polymers:
 Proceed by the stepwise reaction between the functional groups of
reactants.
 The size of the polymer molecules increases at a relatively slow pace.
 Proceeds from monomer to dimer, trimer, tetramer, pentamer, …

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Kinetic Schemes of
Polymerization
 Course Goal

Polymerization
 Kinetic Schemes of Polymerization
The kinetics of polymer synthesis process determines:

- The molecular weight

- The molecular weight distribution
- (The degree of cross-linking)

Key parameters for the material

properties of a polymer!

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 Radical Addition Polymerization
 Radical addition polymerization is initiated by a reactive species R*
produced from some compound I termed an initiator:

 The reactive species, which may be a free radical, cation, or anion, adds
to a monomer molecule by opening the π-bond to form a new radical,
cation, or anion center.
 The process is repeated as many more monomer molecules are
successively added to continuously propagate the reactive center:

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 Radical Addition Polymerization
 Polymer growth is terminated at some point by destruction of the reactive
center (the radical) by an appropriate reaction depending on the particular
reaction conditions.

 Polymer molecular weight = n*M (monomer)

 Steps of:
 Initiation
 propagation
 termination

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 Radical Addition Polymerization
 The C-C double bond in vinyl monomers are the main types of linkages
that undergo radical addition polymerization.

vinyl monomers ethylene

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 Radical Addition Polymerization
Initiation
 Decomposition of initiator
 to yield initiator radicals
 thermally or photo-chemically

Typical Initiators
Reaction

Kinetics

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 Radical Addition Polymerization
Propagation
 The actual polymerization takes place by adding monomers M to the radicals.

Reaction Kinetics

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 Radical Addition Polymerization
Termination
 The polymerization of a chain can be stopped by different mechanisms:
 coupling (or combination)
 disproportionation

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 Radical Addition Polymerization
Termination
 The polymerization of a chain can be stopped by different mechanisms:
 coupling (or combination)
 disproportionation
 Radical Addition Polymerization
Termination
 Other reaction phenomena: Chain transfer
• With solvent: new radical can start new chain

• With ‘regulator’ molecule, to limit molecular weight

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Radical Addition Polymerization
Radical Addition Polymerization
Radical Addition Polymerization
 Condensation Polymerization
 ‘Step-wise’ polymerization
 Much slower than addition polymerization
 A small molecule like water is released
 Monomers with 2 functional groups are required to form linear chains
(thermoplastics)
 More functional groups lead to networks (thermosets)
 There is no real termination -> oligomers can in principle react further
 MW increases as a function of time, but slower and slower the less
monomer is present
 Removal of small molecule helps to enhance reaction
 Mn typically limited to 20, 000 to 30, 000

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 Condensation Polymerization
Example:- Poly Ethylene Terephtalate (PET)
o Two variants:

i) Terephtalic acid + ethylene glycol

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 Condensation Polymerization
Example:- Poly Ethylene Terephtalate (PET)
o Two variants:

i) Terephtalic acid + ethylene glycol

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 Condensation Polymerization
Example:- Poly Ethylene Terephtalate (PET)
o Two variants:

ii) Dimethyl-terephtalate + ethylene glycol

 Condensation Polymerization
 Polycarbonates (PC):
 Diol + phosgene (in presence of NaOH)

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 Condensation Polymerization
 Polycarbonates (PC):
 Diol + phosgene (in presence of NaOH)

Example:

Bisphenol-A Phosgene

Polycarbonate