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POLYMERIC MATERIALS
Diah Susanti, S.T., M.T., Ph.D.
Azzah D. Pramata, S.T., M.T., M.Eng., Ph.D.
MATERIALS AND METALLURGICAL ENGINEERING
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Grading
• Quiz 20%
• Assignments (Presentation, Final Project) 20%
• Middle Examination 30%
• Final Examination 30%
Learning Objective:
Students are be able to....
1. Describe a typical polymer molecule in terms of its
chain structure and, in addition, how the molecule may
be generated from repeat units.
2. Draw repeat units for some polymers
3. Identify and briefly describe:
a) the four general types of polymer molecular structures,
b) the three types of stereoisomers,
c) the two kinds of geometrical isomers, and
d) the four types of copolymers.

MATERIALS AND METALLURGICAL ENGINEERING

What is a polymer?
Poly = Many (more than 1)
Mer = Smallest structure unit/repeating unit of molecule

Possibility to form a polymer:

monomer ➔ dimer ➔ trimer ➔ polymer

POLYMERIZATION
1. Initiation
2. Propagation
3. Termination
Polymer structures
H H
main chain / backbone
Change the
pendant group H ( C C ) H
n end group
will totally
change the H Cl
polymers side group / pendant group

repeat repeat repeat

unit unit unit

H H H H H H H H H H H H H H H H H H

C C C C C C C C C C C C C C C C C C

H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3

Polyethylene (PE) Poly(vinyl chloride) (PVC) Polypropylene (PP)
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All the same monomer
• Monomers all same
type (A)
•A+A+A+A→
• -A-A-A-A-
• Eg. poly(ethene),
polychloroethene,
PVC
Different monomers
• Monomers of two
different types A + B
•A+B+A+B
• → -A-B-A-B-
• Eg. Polyamides,
polyesters
Copolymers
• Copolymers are like polymer alloys.
Different mers are joined to form a mixture
in the backbone, eg. ABS.
• They can be tailored to obtain specific
properties.
 Chemistry and Structure of Polyethylene (PE)

Tetrahedral
arrangement
of C-H

zigzag backbone structure of PE

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Hydrocarbon Molecules
• Many organic materials are hydrocarbons
(composed of hydrogen and carbon).
• Most polymers are made up of H and C.
• The bonds between the hydrocarbon molecules
are covalent.
• Each carbon atom has 4 electrons that may be
covalently bonded, the hydrogen atom has 1
electron for bonding.
• A single covalent bond exists when each of the 2
bonding atoms contributes one electron (ex:
methane, CH4).
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Saturated Hydrocarbons
▪ Each carbon has a
single bond to 4 other
atoms; the 4 valence
electrons are bonded,
the molecule is stable.
Examples are seen in
the table.
▪ The covalent bonds in
each molecule are
strong, but only weak
hydrogen and van der
Waals bonds exist ▪ Most of these hydrocarbons have
between the relatively low melting and boiling points.
molecules. ▪ However, boiling temperatures rise with
increasing molecular weight.
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Unsaturated Hydrocarbons
• Double & triple bonds are somewhat unstable – involve
sharing 2 or 3 pairs of electrons, respectively. They can
also form new bonds
• Double bond found in ethylene - C2H4
H H
C C
H H

• Triple bond found in acetylene - C2H2

H C C H
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So, what is the difference

between saturated and
unsaturated hydrocarbons ???
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Isomerism ???
• Two compounds with same chemical formula can have
different structures (atomic arrangements).
for example: C8H18
• normal-octane
H H H H H H H H
H C C C C C C C C H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
H H H H H H H H

H3C ( CH2 ) CH3
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• 2,4-dimethylhexane
CH3
H3C CH CH2 CH CH3
CH2
CH3
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POLYMER + IZATION ???

POLYMERIZATION ???

A Process of forming “long chain”

polymer from ‘mers’ (by linking
smaller molecules to make larger
molecules)
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Polymerization (generally) devided in two

process:
1. Addition Polymerization
2. Condensation (Step) Polymerization
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1.Addition (chain) Polymerization

Definition: a very fast (in few seconds) chain reaction
polymerization initiated by free radical (partikel reaktif yang
mengandung elektron tak berpasangan) or ions.
Polimer penting yang dihasilkan melalui polimerisasi adisi
adalah turunan etena berbentuk CH2=CHX atau
CH2=CXY, yang disebut monomer vynil.

1.1 Free Radical Polymerization

1.2 Ionic (Kation, Anion) Polymerization
1.1 Free Radical Polymerization
Free radical polymerization: ethylene gas reacts with the initiator
(catalyst). (“R.” is the unpaired electron)

Reactive
– Initiation
monomer

Reactive
– Propagation dimer

– Termination
Polymer
product
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1.2 Ionic (Kation, Anion) Polymerization (next meeting)

 2. Condensation (Step) Polymerization
M.A Cowd (1991), stated: polimerisasi kondensasi yaitu
polimerisasi yang terjadi pada saat zat bermassa molekul rendah,
dimana terjadi reaksi antara dua molekul bergugus fungsi banyak
(molekul yang mengandung dua gugus fungsi atau lebih yang dapat
bereaksi) dan terbentuk satu molekul besar bergugus fungsi banyak,
disertai penyingkiran molekul kecil (seperti air).

dipanasi
bersama sedikit
asam sulfat
pekat

CH3COOH + C2H5OH ========> CH3COOC2H5 + H2O

asam etanoat ester etil etanoat
etil alkohol
(asam asetat) (etil asetat)

Only has one functional moeity 21

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Only has one functional moeity

Condensation (step) polymerization occured step by step (not directly)

forming a large chain polymer.
The preceding reactions are only one step polymerization, because the
reactants only has one functional moity.
Homework 1: Find the cases of condensation (step) polymerization
that has double/triple/more steps of polymerization.
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Some Common Addition Polymers
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MOLECULAR WEIGHT
• Molecular weight, M: Mass of a mole of chains.

Low M

high M

• Polymers can have various lengths depending on the

number of repeat units.
• During the polymerization process not all chains in a polymer
grow to the same length, so there is a distribution of
molecular weights. There are several ways of defining an
average molecular weight.
• The molecular weight distribution in a polymer describes the
relationship between the number of moles of each polymer
species and the molar mass of that species.
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Degree of Polymerization, DP
DP = average number of repeat units/mol
Mn
DP =
m
Mn = the number average molecular weight (mass)
m = molecular weight

Ex. problem,
for PVC: m = 2(carbon) + 3(hydrogen) + 1(Clorine)
(from front of book) = 2(12.011) + 3(1.008) + 1(35.45)
= 62.496 g/mol (mass/mol of 1 mer)
DP = 21,150 / 62.496 = 338.42
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Polymer Chain Lengths

• Many polymer properties are affected by the length of the
polymer chains. For example, the melting temperature
increases with increasing molecular weight as the effect of
increasing polymer chains.
• At room temp, polymers with very short chains (roughly 100
g/mol) will exist as liquids.
• Those with weights of 1000 g/mol are typically waxy solids
and soft resins.
• Solid polymers range between 10,000 and several million
g/mol.
• The molecular weight affects the polymer’s properties
(examples: elastic modulus & strength).
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Polymers – Molecular Shape

• Straight (b) and twisted (c) chain segments are generated

when the backbone carbon atoms (dark circles) are oriented
as in the figure above.
• Chain bending and twisting are possible by rotation of carbon
atoms around their chain bonds.
• Some of the polymer mechanical and thermal characteristics
are a function of the chain segment rotation in response to
applied stresses or thermal vibrations.
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Chain End-to-End Distance, r

• Representation of a single
polymer chain molecule that
has numerous random kinks
and coils produced by chain
bond rotations; it is very
similar to a heavily tangled
fishing line.
• “r” is the end to end distance
of the polymer chain which is
much smaller than the total
chain length.
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Molecular Structures for Polymers

secondary
bonding

Linear Branched Cross-Linked Network

• The physical characteristics of a polymer depend

also on differences in the structure of the molecular
chains (other variables are shape and weight).
• Linear polymers have repeat units joined end to end
in single chains. There may be extensive van der
Waals and hydrogen bonding between the chains.
Examples: polyethylene, PVC, nylon.
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Molecular Structures- Branched

Linear Branched Cross-Linked Network

• Where side-branch chains have connected to main chains,

these are termed branched polymers. Linear structures may
have side-branching.
• HDPE – high density polyethylene is primarily a linear
polymer with minor branching, while LDPE – low density
polyethylene contains numerous short chain branches.
• Greater chain linearity and chain length tend to increase the
melting point and improve the physical and mechanical
properties of the polymer due to greater crystallinity.
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Molecular Structures –Cross-linked, Network

secondary
bonding

Linear Branched Cross-Linked Network

• In cross-linked polymers, adjacent linear chains are

joined to one another at various positions by
covalent bonding of atoms. Examples are the
rubber elastic materials.
• Small molecules that form 3 or more active covalent
bonds create structures called network polymers.
Examples are the epoxies and polyurethanes.
• Fig. 1-2. The interrelation of the states of bulk polymers.
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Plastic Recycling Symbols

In 1988 the Society of the Plastics Industry
developed a numeric code to provide a uniform
convention for different types of plastic containers.
These numbers can be found on the underside of
containers.
1. PET; PETE (polyethylene terephthalate): plastic water and
soda bottles.
2. HDPE (high density polyethylene): laundry/dish detergent
3. V (Vinyl) or PVC: Pipes, shower curtains
4. LDPE (low density polyethylene): grocery bags, sandwich
bags
5. PP (polypropylene): Tupperware®, syrup bottles, yogurt cups,
6. PS (polystyrene): Coffee cups, disposable cutlery
7. Miscellaneous: any combination of 1-6 plastics
Learning Objective:
Students are be able to....
1. Describe a typical polymer molecule in terms of its
chain structure and, in addition, how the molecule may
be generated from repeat units.
2. Draw repeat units for some polymers
3. Identify and briefly describe:
a) the four general types of polymer molecular structures,
b) the three types of stereoisomers,
c) the two kinds of geometrical isomers, and
d) the four types of copolymers.

MATERIALS AND METALLURGICAL ENGINEERING

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2nd INDIVIDUAL ASSIGNMENT….

Please submit your work before
TUESDAY, Feb 24st

Submit to:
azzah.pramata@gmail.com

Subject : Name_NRP_Asgn 1