POLYMER PROCESS Dr Wan Zaireen Nisa

Yahya
ENGINEERING Email: zaireen.yahya@utp.edu.my

CDB4423 Office: 05-3687584 ( 04-03-24)

1
 CDB 4423
POLYMER
PROCESS
ENGINEERING
n

Chapter 2:
Polymerisation,
Molecular weight
& structure

2
 1. Polymerisation Method:
i. Addition Polymerisation
ii. Condensation Polymerisation

CONTENTS 2. Molecular Weight and Molecular

Weight Distribution
3. Effect of molecular weight

3
LESSON OUTCOME
At the end of this lecture, students should be able to;
•Describe the two types of polymerization, addition and
condensation polymerization
•Calculate molecular weight, Mn, Mw, polydispersity
•Understand the effect of molecular weight on the
properties and processability of the polymer

4
POLYMERIZATION
5
 POLYMERIZATION
• There are two major classes of polymer formation mechanisms
– Addition polymerization:
The polymer grows by sequential addition of monomers to a
reactive site
• Chain growth is linear
• Maximum molecular weight is obtained early in the reaction
– Condensation Polymerization/Step-Growth polymerization:
Monomers react together to make small oligomers. Small
oligomers make bigger ones, and big oligomers react to give
polymers.
• Chain growth is exponential
• Maximum molecular weight is obtained late in the reaction

6
7
 Polymerization Methods
i. Addition polymerization
A. Free Radical Polymerization
1. Initiation H H Radical
H H
R R C C
transferred
Free radical C C
initiator (unpaired H H H H
electron)
monomer

R
R

H H H
C C C C
sp2 carbons
H H H H
H
s bonds sp3 carbon
p bond
8
 Polymerization Methods
A. Free Radical Polymerization
H H
2. Propagation C C
H H
H H H H H H H H H H H H
H H
R C C C C R C C C C R C C C C C C
H H H H H H H H H H H H
H H

H H
C C

H H
R

Both carbon atoms will

H
change from sp2 to sp3.
C C

H H
H

9
 Polymerization Methods

A. Free Radical Polymerization

3. Termination

H H H H
R C C + R R C C R
H H H H

H H H H H H H H
R C C + R C C R C C C C R
H H H H H H H H

Intentional or unintentional molecules/impurities can also terminate.

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 Addition Polymerization

A *A A A A A
m

In A A A A A In A A A A A
n
n
A* B A A A A
m
Chain Transfer Disproportionation
New reactive site
is produced
Termination
Reactive site is consumed
MW

0 100
11
% conversion
ii. Condensation or Step-Growth Polymerization
Stage 1
n n
Consumption
of monomer

Stage 2

Combination
of small fragments

Stage 3

Reaction of
oligomers to give
high molecular
weight polymer

12
 Step-Growth Polymerization
• Because high polymer does not form until the end of
the reaction, high molecular weight polymer is not
obtained unless high conversion of monomer is
achieved.
1000

Degree of Polymerization

1
100 Xn 
1 p
Xn = Degree of polymerization
p = mole fraction monomer 10
conversion


1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction Conversion (p)
13
 Nylon-6,6
O O O O
NaOH
Cl Cl H2N NH2 H
4 4 Cl 4
N 4 N
H H
Adipoyl chloride 1,6-Diaminohexane

O O
H
Adipoyl chloride HO 4
N 4 N
in hexane H H n

Nylon 6,6 6 carbon 6 carbon

diacid diamine
Nylon-6,6
Diamine, NaOH, in H2O

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 Nylon-6,6
Since the reactants are in different
phases, they can only react at the
phase boundary. Once a layer of
polymer forms, no more reaction
occurs. Removing the polymer
allows more reaction to occur.

Adipoyl chloride
in hexane

Nylon 6,6

Diamine, NaOH, in H2O

15
MOLECULAR WEIGHT AND
MOLECULAR WEIGHT
DISTRIBUTION 16
 POLYETHYLENE (PE)

What is n? (some use m)

n is degree of polymerisation

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 Degree of Polymerization, DP
DP = average number of repeat units per chain
Mn
DP 
n
where n  repeat unit molecular weight

Example:
for PVC: what is the DP if Mw =21150 g/mol
n = 2(carbon) + 3(hydrogen) + 1(Clorin)
= 2(12.011) + 3(1.008) + 1(35.45)
= 62.496 g/mol
DP = 21,150 / 62.496 = 338.42 18
 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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 Effect of Molecular weight
Effect on:
• melting point 145 C for polyethylene

Melting temperature
• the degree of polymer
entanglement
• the degree of intermolecular
interactions
H – (CH2)n – H
• At room T, polymers with :
• very short chains
(roughly 100 g/mol) will
exist as liquids Molecular weight
• weights of 1000 g/mol
are typically waxy solids
and soft resins.
• range between 10,000 Tensile strength
and several million g/mol
are solid polymers.
• physical and mechanical
properties
• tensile strength
• melt-processing conditions Molecular weight
• application 20
 Molecular weight: a few definitions
Synthetic polymers are polydisperse, i.e. a given polymer sample exhibit
distribution of molecular weights

Mi molecular weight of ith polymer chain

Mn Ni number of polymer chains with molecular weight Mi
wi weight fraction of polymer chains with molecular weight Mi
Mw
wi

__ M N i i
Mn number average molecular weight Mn  i
Mz N i
kinetics i

Mi
N M
2
__ i i
Mw weight average molecular weight Mw  i

Ð = Mw /Mn
load-bearing properties
N Mi
i i

dispersity (1 – 10)
N M
3
__ i i
Mz or Z-average molecular weight Mz  i

N M
2
expresses all the features i i
melt viscosity i
- kinetics 1
  Ni M i  1
 
- processing __
 
M viscosity average molecular weight M   i 
- properties

2
Ni M i
Mn < M < Mw  i 21 
(0 <  < 1)
Molecular Weight, and

Molecular weight average that are commonly used:

• The first is the Number Average Molecular Weight ( )

• The second is the Weight Average Molecular Weight ( )

• Another important aspect of the molecular weight

distribution is the shape of the curve.

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 Molecular Weights
Not only are there different structures (molecular arrangements)
…… but there can also be a distribution of molecular weights
(i.e. number of monomers per polymer molecule).

20 mers 16 mers

10 mers

20  16  10
Average molecular weight = M monomer  15.3M monomer
3
This is what is called number average molecular weight. (Mn)

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Molecular Weight
• The figure to the right
represents a typical molecular
weight distribution.

• The vertical axis represents the

number of chains at that length.
• The horizontal axis represents
the different chain lengths.
Notice that the longer chains are to the left
on the graph and the shorter chains are
to the right.

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Molecular Weight
• The Number Average Molecular
• Weight ( ) is the total
weight of the polymer
molecules divided by the total
number of polymer molecules.

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Molecular Weight
Number Average Molecular Weight ( )
Example:
We have:
10 moles of Polyethylene (PE) that are 500 monomers long
5 moles of PE that are 100 monomers long
5 moles of PE that are 800 monomers long

What is ?
Molecular Weight
Number Average Molecular Weight ( )
Example:
Each monomer is 2 Carbons and 4 Hydrogens
10 moles X 500 monomers = 5,000
5 moles X 100 monomers = 500
5 moles X 800 monomers = 4,000
Total number of moles = 20 = (10 + 5 + 5)
Total number of monomers = 9,500

What is ? 9500/20 = 475 monomers

The average chain is 475 monomers long
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Molecular Weight
Look at the numbers from the previous example:
10 moles of PE that are 500 monomers long
5 moles of PE that are 100 monomers long
5 moles of PE that are 800 monomers long

Calculate the

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 Average Mass Molecular Weight, Mw

Calculate the Mw
Find the weight fractions:
10 x 500 / 9500 = 52.6%
5 x 100/ 9500 = 5.3%
5 x 800 / 9500 = 42.1%

Mw = (0.562 x 500) + (0.053 x 100) + (0.421 x 800) =

605.3 monomers long

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Molecular Weight
• The Weight Average
Molecular Weight ( )
takes into account that the
larger molecules contain a
much higher amount of
the molecular mass of the
polymer.
• The Weight Average
Molecular Weight is
almost always higher than
the Number Average
Molecular Weight ( ).

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MOLECULAR WEIGHT

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 MOLECULAR WEIGHT DISTRIBUTION
Molecular Weight
• Just knowing the averages is
not enough, the distribution
of the molecular weights
also has a large effect on
how the material will
process and its properties.
• A broader or ‘wide spec’
distribution may make the
material unsuitable for
processes like injection
molding, but better suited
for processes like extrusion,
blow-molding, or
thermoforming.

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Molecular Weight
• For injection molding
grades of material, a
narrower distribution
is better.
• When the distribution
is narrow, the polymer
chains will melt and
flow at around the
same temperature.
• The longer the chains,
the higher the viscosity
or resistance to flow.

•33
Molecular Weight
• When you have a broad or
even a bi-modal distribution,
the shorter chains melt more
quickly and allow some flow,
while the longer chains hold
the material together.
• This gives the polymer mixture
melt strength which allows it
to be used for some of the
other processes mentioned
other than injection molding.

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Molecular Weight
• You can have virtually
an infinite number or
distributions with the
same number average
molecular weight.

• All of these materials

will process differently
and have at least
slightly different
properties.

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Properties
When making polymers, the goal is to make a material with
the ideal properties.

The longer the molecules (or the higher the molecular weight)
the higher the entanglement forces:
• Longer hair is harder to get untangled than shorter
hair

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Properties
•Increasing the molecular weight of the material increases
many of the properties of the material by increasing the
entanglement of the molecules.
•A higher molecular weight:
•Increases the chemical resistance - to a point
– It takes more damage to the main chains of the
molecules before it will affect the strength of the
material
– The big loophole to this is if you have a chemical
• that is very similar to the chemical makeup of the
main chain, it will dissolve it much more easily
»Like Dissolves Like

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Properties
A higher molecular weight:
•Increases how far the material can stretch before
rupturing (ductility)
– The higher degree of entanglement allows the
material to be pulled further before the chains break

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Properties
A higher molecular weight:
– Increases ductility: A candle and Polyethylene (PE) have
basically the same molecular structure. The chain length of
the candle is just much shorter than that of the PE. If you
bend a bar of PE in half – it will bend, if you bend a candle in
half, it will fracture.

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Properties
• Processors want materials that will flow easily in order to form
complex geometries, but that can affect the properties of
material used to create the product.

• Many times it turns out to be a trade-off between the required

properties and processability of the material.

• CD’s and DVD’s are made from the same material as most safety
glasses, Polycarbonate.

• Safety glasses require a higher molecular weight in order to

provide the necessary property of impact resistance.
• CD’s and DVD’s require a lower molecular weight material in
order to fill out the thin walls. CD’s and DVD’s can shatter, safety
glasses don’t.

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Properties

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Molecular weight: characterization techniques
Mn  techniques related to colligative properties (dependence on the number of
molecules)
▪ membrane osmometry (> 25 000 g/mol)
▪ vapor pressure osmometry (< 25 000 g/mol)
 mass spectrometry
▪ electrospray ionization mass spectrometry (ESI-MS)
▪ matrix-assisted laser desorption/ionization (MALDI)
 size exclusion chromatography
Mn
Mw  static laser light scattering
 analytical ultracentrifuge Mw
 size exclusion chromatography

wi
Mz  static laser light scattering Mz
 analytical ultracentrifuge
 size exclusion chromatography
Mi

M  viscometry
 size exclusion chromatography
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MOLECULAR WEIGHT
Property/process parameters Increase the
MW
Tensile strength increase
Impact strength increase
Brittleness decrease
Abrasion resistance increase
Melt viscosity increase
Processing temperature increase

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Gel Permeation Chromatography Theory

• Used to separate liquid phase components

• Form of size exclusion chromatography where small MW components trapped
in gel, higher MW components too large, pass around, come out faster

• Can estimate MW of unknowns by running standards of known MW

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Molecular Weight Distribution Comparison
by Gel Permeation Chromatography
Mw = 73800, Mn = 37400, MWD = 2.0

Mw = 124600, Mn = 33200, MWD = 3.8

16 18 20 22 24 26 28
ELUTION VOLUME (mls)

Increasing Molecular Weight

* Trademark of The Dow Chemical Company 45

 Properties: Molecular weight
synthetic polymers possess a molecular weight
distribution

Ni

Mi

 N iM i
2
N M i i
polydispersity index = Mw/Mn
Mw  i
Mn  i

N M i i N i
i
i

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 Molecular weight and dispersion
Synthetic polymers always show a distribution in molecular
weights.
number average : M n   n i Mi
n i

weight average: Mw 
 w M n M M
 i i i i i

w n M i i i

(ni and wi are number and weight fractions, respectively, of

molecules with molar mass Mi)

The polydispersity index is given by Mw /Mn

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 Molecular weight and dispersion -
an example:
Here are:
10 chains of 100 molecular weight
20 chains of 500 molecular weight
40 chains of 1000 molecular weight
5 chains of 10000 molecular weight

(10 100)  (20  500)  (40 1000)  (5 10000)

Mn   1347
10  20  40  5

(10 1002 )  (20  5002 )  (40 10002 )  (5 100002 )

Mw   5390
(10 100)  (20  500)  (40 1000)  (5 10000)

Mw
Polydispersity  4
Mn
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 What the Weights Mean
Mn: This gives you the true average weight

Let's say you had the following polymer sample:

2 chains: 1,000,000 Dalton 2,000,000
5 chains: 700,000 Dalton 3,500,000
10 chains: 400,000 Dalton 4,000,000
4 chains: 100,000 Dalton 400,000
2 chains: 50,000 Dalton 100,000
10,000,000
10,000,000/23 = 435,000 Dalton

1 Dalton = 1 g/mole

49
 Weight Average Molecular Weight
Mw: Since most of the polymer mass is in the heavier fractions, this gives
the average molecular weight of the most abundant polymer fraction by
mass.

2,000,000
 0.20  1,000,000  200,000
10,000,000
3,500,000
 0.35  700,000  245,000
10,000,000
4,000,000
 0.40  400,000  160,000
10,000,000
400,000
 0.04  100,000  4,000
10,000,000
100,000
 0.01 50,000  500
10,000,000
Total  609,500

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 Molecular Weights
Why do we care about weight average MW?
-some properties are dependent on MW (larger MW polymer chains can
contribute to overall properties more than smaller ones).

Distribution of
polymer weights

Examples –
Light scattering: larger molecules scatter more light than smaller ones.

Infrared absorption properties: larger molecules have more side

groups and light absorption (due to vibrational modes of side groups)
varies linearly with number of side groups.
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 Polydispersity and Degree of Polymerization
Mw
Polydispersity: 1
Mn

When polydispersity = 1, system is monodisperse.


Degree of Polymerization:

Mn
Number avg degree of polymerization nn 
mo
Mw
Weight avg degree of polymerization nw 
mo

52
 Example 1
Compute the number-average degree of polymerization for polypropylene,
given that the number-average molecular weight is 1,000,000 g/mol.

What is “mer” of PP? C3H6

Mer molecular weight of PP is mo=3AC+6AH

=3(12.01 g/mol)+6(1.008 g/mol)
= 42.08 g/mol

Number avg degree of polymerization

Mn 106 g / mol
nn    23,700
mo 42.08g / mol

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 Problem 1 (a, b, and c)
A. Calculate the number and weight average degrees of polymerization
and polydispersity for a polymer sample (PP) with the following
distribution.

Avg # of monomers/chain Relative abundance

10 5
100 25
500 50
1000 30
5000 10
50,000 5

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 Problem 2 (b)
B. If the polymer is PMMA: number and weight average degrees of
polymerization

CH3
|
-CH2-C-
|
CO2CH3

Mw if monomer is methylmethacrylate (5C, 2O, and 8H)

So m0= 5(12)+2(16)+8(1)= 100 g/mol

55
 Problem 3 (c)
C. If we add polymer chains with avg # of monomers = 10 such that their
relative abundance changes from 5 to 10, what are the new number
and weight average degrees of polymerization and polydispersity?

Add 5 more monomers of length 10 ….

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 Polymer Molecular Configurations
• Regularity and symmetry of side groups affect properties

Can it crystallize?
Melting T?
Polymerize

• Stereoisomerism: (can add geometric isomerism too)

Syndiotactic
Alternating sides

Isotactic Atactic
On one side Randomly placed

- Conversion from one stereoisomerism to another is not possible by simple

rotation about single chain bond; bonds must be severed first, then reformed!

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 Polymer Geometrical Isomerism
• Regularity and symmetry of side groups affect properties

H H

cis-structure trans-structure

with R= CH3 to form rubber

Cis-polyisoprene trans-polyisoprene

-Conversion from one isomerism to another is not possible by

simple rotation about chain bond because double-bond is too
rigid!

58
 Polymer Microstructure
• Covalent chain configurations and strength:
More rigid
Van der Waals, H

Direction of increasing strength

Adapted from Fig. 14.7, Callister 6e.

Long branching Short branching Star branching Dendrimers

59
 CoPolymers
• Random, Alternating, Blocked, and Grafted

• Synthetic rubbers are often copolymers.

e.g., automobile tires (SBR)

Styrene-Butadiene Rubber random polymer

60
 Example 3
Nitrile rubber copolymer, co-poly(acrylonitrile-butadiene), has

Mn  106,740g / mol nn  2000

Calculate the ratio of (# of acrylonitrile) to (# of butadiene).


3 C = 3 x 12.01 g/mol
3 H = 3 x 1.008 g/mol  4 C = 4 x 12.01 g/mol
6 H = 6 x 1.008 g/mol
1 N = 1 x 14.007 g/mol
m2= 54.09 g/mol
m1= 53.06 g/mol
1,4-addition product

Mn 106,740
We need to use an mo    53.57g / mol
nn 2000
avg. monomer MW:
mo  f1m1  f2m2  f1(m1  m2 )  m2

 f2 0.7
m0  m2 53.57  54.09
f1    0.7 f2  1 f1  0.3  7 :3

m1  m2 53.06  54.09 f1 0.3
61
 Vulcanization
• Crosslinking in elastomers is called vulcanization, and is achieved by
irreversible chemical reaction, usually requiring high temperatures.

• Sulfur compounds are added to form chains that bond adjacent

polymer backbone chains and crosslinks them.
• Unvulcnaized rubber is soft and tacky an poorly resistant to wear.

e.g., cis-isoprene Single bonds

(S)m
Double bonds+ (m+n) S
(S)n

Stress-strain curves
62
 Molecular Weight and Crystallinity
• Molecular weight, Mw: Mass of a mole of chains.

• Tensile strength (TS):

--often increases with Mw.
--Why? Longer chains are entangled (anchored) better.

• % Crystallinity: % of material that is crystalline.

--TS and E often increase
with % crystallinity.
--Annealing causes crystalline
crystalline regions to grow. region
% crystallinity increases.
amorphous
region

Adapted from Fig. 14.11, Callister 6e. 63

 Polymer Crystallinity

Polyethylene • Some are amorphous.

• Some are partially crystalline (semi-crystalline).
• Why is it difficult to have a 100% crystalline polymer?

c (s  a )
%crystallinity   100%
s (c  a )

s = density of specimen in question

a = density of totally amorphous polymer
c = density of totally crystalline polymer

64
 Polymer Crystallinity
Degree of crystallinity depends on processing conditions (e.g. cooling
rate) and chain configuration.

Cooling rate: during crystallization upon cooling through MP, polymers

become highly viscous. Requires sufficient time for random &
entangled chains to become ordered in viscous liquid.

Chemical groups and chain configuration:

More Crystalline Less Crystalline

Smaller/simper side groups Larger/complex side groups
Linear Highly branched
Crosslinked, network
Isotactic or syndiotactic Random

65
 Semi-Crystalline Polymers
Fringed micelle model: crystalline region embedded in amorphous
region. A single chain of polymer may pass through several
crystalline regions as well as intervening amorphous regions.

s  a
fc 
c  a

Crystalline volume fractions Important



66
 Packing of Polymers
• Packing of “spherical” atoms as in ionic and metallic
crystals led to crystalline structures.

• How polymers pack depend on many factors:

• long or short, e.g. long (-CH2-)n.
• stiff or flexible, e.g. bendy C-C sp3.
• smooth or lumpy, e.g., HDPE.
• regular or random
• single or branched
• slippery or sticky, e.g. C-H covalent (nonpolar) joined
via vdW.

Analogy: Consider dried (uncooked) spaghetti (crystalline)

vs. cooked and buttered spaghetti (amorphous).
• pile of long “stiff” spaghetti forms a random
arrangement.
• cut into short pieces and they align easily.
Candle wax more crystalline than PE, even though
same chemical nature. 67
 What Are Expected Properties?
• Would you expect melting of nylon 6,6 to be lower than PE?
H  O H  O
nylon 6,6 H H
  ||  |  || polyethylene
|
    C C
 N  C   N  C  C   N  C 
    H H
| |  |  |  |
H H 
6 H 
H 
4 H
+ +
+ + +
+ Van der Waals bonds
Hydrogen bonds + + +
 + +  +

H  O H  O H H
  ||  |  ||
|
    C C
 N  C   N  C  C   N  C 
    H H
| |  |  |  |
H H 
6 H 
H 
4 H

a) 
What is the source of intermolecular cohesion in Nylon vs PE?
 b) How does the source of linking affect temperature?

With H-bonds vs vdW bonds, nylon is expected to have (and does)

higher melting T. 68
 What Are Expected Properties?
Which polymer more likely to crystallize? Can it be decided?

Linear syndiotactic polyvinyl chloride Linear isotactic polystyrene

• For linear polymers, crystallization is more easily accomplished as

chain alignment is not prevented.
• Crystallization is not favored for polymers that are composed of
chemically complex mer structures, e.g. polyisoprene.

• Linear and syndiotactic polyvinyl chloride is more likely to

crystallize.
• The phenyl side-group for PS is bulkier than the Cl side-group for
PVC.
• Generally, syndiotactic and isotactic isomers are equally likely to
69
crystallize.
 What Are Expected Properties?
Which polymer more likely to crystallize? Can it be decided?
Networked Linear and highly crosslink
Phenol-Formaldehyde cis-isoprene
(Bakelite)

+
H
+ H20

• Networked and highly crosslinked structures are near

impossible to reorient to favorable alignment.

• Not possible to decide which might crystallize. Both not

likely to do so.

70
 Polymer Microstructure
Polyolefins with side chains have stereocenters on every other carbon

CH3
n
CH3 CH3 CH3 CH3 CH3 CH3 CH3

With so many stereocenters, the stereochemistry can be complex. There are

three main stereochemical classifications for polymers.

Atactic: random orientation

Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

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 Tacticity
Tacticity – stereoregularity of chain
H H H H H H H H
isotactic – all R groups on
C C C C C C C C
same side of chain
H R H R H R H R

syndiotactic – R groups H H H R H H H R
alternate sides C C C C C C C C
H R H H H R H H

H H H H H R H H
atactic – R groups random C C C C C C C C
H R H R H H H R
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 Why is this important?
• Tacticity affects the physical properties
– Atactic polymers will generally be amorphous, soft,
flexible materials
– Isotactic and syndiotactic polymers will be more
crystalline, thus harder and less flexible
• Polypropylene (PP) is a good example
– Atactic PP is a low melting, gooey material
– Isoatactic PP is high melting (176º), crystalline, tough
material that is industrially useful
– Syndiotactic PP has similar properties, but is very
clear. It is harder to synthesize

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 LINEAR POLYMERS WITH SIDE BRANCHES
Isotactic Atactic
• Same side of the linear • Irregular points on both sides
polymer of the linear polymer
• Greater effect of • Chains of molecules cannot
dispersion forces get close together, therefore
therefore high density, low density.
rigid and tough and a high • Soft, waxy – little use
softening temp.

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POLY(PROPENE)
•This varying degree of randomness will affect the
strength and melting point of the polymer.

•The less random, the stronger the polymer and the

higher the melting point

•This is because in a more ordered polymer they chains

can get closer together and hence the van der Waal’s
forces will be greater.

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HOMEWORK
1. During normal operation Melt index is used to check the MW,
explain why.
2. Explain how MW of PE is controlled under the following
condition:
a. Initiator such as peroxide is used
b. Catalyst is used
3. Why broad and narrow MWD Polymer products are
produced
4. Name three processing/fabrication equipment and the
application or targeted market
5. Explain TWO reason for copolymerization

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SUMMARY
•In the addition polymerization, the polymers are
synthesized by the addition of unsaturated monomers to
the growing chain, i.e Polyethylene,
•For condensation polymerization, two functional units
combined to form a monomer then polymerize in step
growth, splitting off a small molecule usually water, i.e
polyester, polyamide
•The molecular weight, Mn, Mw, molecular weight
distribution will effect the properties and processability
of the polymer

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