POLYMER ENGINEERING

ChE (411)
Lecture # 4

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5.5 The following table lists molecular weight data for a polypropylene material. Compute (a) the
number-average molecular weight, (b) the weight-average molecular weight, and (c) the degree
of polymerization.

Molecular Weight
Range (g/mol) xi wi
8,000–16,000 0.05 0.02
16,000–24,000 0.16 0.10
24,000–32,000 0.24 0.20
32,000–40,000 0.28 0.30
40,000–48,000 0.20 0.27
48,000–56,000 0.07 0.11

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(a) From the tabulated data, we are asked to compute M n , the number-average molecular weight. This
is carried out below.

Molecular wt
Range Mean Mi xi xiMi
8,000–16,000 12,000 0.05 600
16,000–24,000 20,000 0.16 3200
24,000–32,000 28,000 0.24 6720
32,000–40,000 36,000 0.28 10,080
40,000–48,000 44,000 0.20 8800
48,000–56,000 52,000 0.07 3640
Mn = ∑xM i i = 33, 040 g/mol

(b) From the tabulated data, we are asked to compute M w , the weight-average molecular weight.

Molecular wt.
Range Mean Mi wi wiMi
8,000–16,000 12,000 0.02 240
16,000–24,000 20,000 0.10 2000
24,000–32,000 28,000 0.20 5600
32,000–40,000 36,000 0.30 10,800
40,000–48,000 44,000 0.27 11,880
48,000–56,000 52,000 0.11 5720
Mw = ∑ wi M i = 36,240 g/mol

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(c) Now we are asked to compute the degree of polymerization, which is possible using Equation 5.6.
For polypropylene, the repeat unit molecular weight is just

m = 3(AC) + 6(AH)

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

And
Mn 33,040 g/mol
DP = = = 785
m 42.08 g/mol

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Polymerization Addition

Free radial polymerization

Initiation Propagation Termination

Catalyst peroxide

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  Free-Radical Polymerization

Free radical polymerization are chain

polymerizations in which each polymer molecule
grows by addition of monomer to a terminal free-
radical reactive site known as an active center.
Consequent upon every addition of monomer, the
active center is transferred to the newly-created chain
end.
Free-radical polymerization is the most widely
practiced method of chain polymerization and is used
almost exclusively for the preparation of polymers
from monomers of the general structure.

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 Initiation
 Initiation involves creation of the free-radical active
center and takes place in two steps:
 Formation of free radicals from an initiator.
 Addition of one of these free radicals to a molecule
of monomer.
 Two principle ways to form free radicals:
 Homolysis (Homolytic Scission) of a single bond
 Single electron transfer to or from an ion or
molecule (redox reactions)

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 Homolysis effected by the application of heat (∆) and many
compounds particularly peroxide (-O-O-) or azo (-N=N-)
linkages.
O O O

C O O C 2 C O.

Benzoyl Peroxide Benzoyloxy radicals

(CH3)3C O OH (CH3)3C O. + .
OH

t-butyl hydroperoxide t-butoxy radical Hydroxy radical

Many radicals produced undergo further breakdown before reaction with

monomer
O O

C O. . + C

O
Phenyl radical Carbon dioxide

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Redox reactions perform polymerizations at low temperature e.g.
CH3 CH3

C O OH + Fe 2+
C
.
O + OH + Fe3+

CH3 CH3
Cumyl hydroperoxide Ferrous ion Cumyloxy radical Hydroxyl ion Ferric ion

Active center is created when a free radical (R.) generated from

an initiator attacks the π-bond of a molecule of monomer
R CH2 CH

.
R + H2C CH X

X R CH CH2

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 Propagation
Propagation involves the growth of the polymer chain by rapid
sequential addition of monomer to the active center

R CH2 CH CH2 CH

X X

R CH2 CH + CH2 CH Head-to-tail addition

X X
R CH2 CH CH CH2

X X

Head-to-head addition

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 Termination
 Two most common mechanisms of termination involve
bimolecular reaction of growing chain polymer chains.
 Combination involves the coupling together of two growing
chains to form a single polymer molecule.
CH2 CH + HC CH2 CH2 CH CH CH2

X X X X

 Hydrogen atom can be abstracted from one growing chain by

another in a reaction known as disproportionation

CH2 CH + HC CH2 CH2 CH2 + CH CH

X X X X

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 Polymerization

Addition

Cationic polymerization + anionic polymerization -

Initiation Propagation Termination

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 Ionic Polymerization
 Chain Polymerization of olefinic monomers can also be
effected via active centres which possess an ionic charge.
 There are two types of ionic polymerization:
 Ionic polymerization in which the active centre is
positively charged are called as cationic polymerization.
 For cationic active centers- CH2 CHX polymerization will
proceed if the substituent group X is able to donate electron
and/or delocalize the positive charge.
 Ionic Polymerization in which the active centre is
negatively charged are called as anionic polymerization.
 For anionic active centres- CH2 CHXthe substituent group
must be able to withdraw electrons and/or delocalize the negative
charge.

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Most monomers cannot be polymerized both by cationic and by
anionic polymerization

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 Initiation

Cationic active centres are created by reaction of monomer

with electrophiles (e.g. R+). Protonic acids such as
sulphuric acid(H2SO4) and perchloric acid (HClO4) are of
use as initiators and involve proton(H+) as addition.
 Hydrogen halide acids(e.g. HCl) are not suitable as
initiators because the halide counter-ion rapidly combines
with the carbocationic active centre to form a stable
covalent bond.
 Lewis acids such as BF3, AlCl3, and SnCl4 are most
important initiators but must be used in conjunction with a
co-catalyst which very often is water but also can be an
acid or an organic halide.

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 BF3 + H2O H+(BF3OH)-

AlCl3 + RCl R+(AlCl4)-

For BF3/H2O system, the 2nd step of initiation

H+(BF3OH)- + H2C CR1R2 H3C CR1R2 (BF3OH)-

In general, the 2nd step of initiation can be represented by

R+A- + H2C CR1R2 R H2C CR1R2 A-

Where R+ is the electrophile and A- is the counter ion

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 Propagation

 Propagation proceeds predominantly through successive

head-to-tail additions of monomer to the active centre
same as free-radical polymerization.

CH2 CR1R2 A- + H2C CR1R2 H2C R2R1C H2C CR1R2 A-

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 Polyaddition
 Step polymerizations in which monomers react together
without elimination of other molecules.
 Polyurethanes by the RA2 + RB2 reaction of diisocyanates
with diols is one of few important examples of linear
polyaddition.

nO C N R1 N C O + nHO R2 OH

O O

H
[ C N R1 NH C O R2 O ]n

Polyureas Diisocyanates with diamines

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 TERM PAPER
This task should submit as (softcopy, word file).
1- Polymer definitions.
2- Examples.
3- Advantages of polymers.
4- Uses and applications.
* Thermal Response and line structure Types
• Definitions
• Examples
• Talk about Malting temperature and glass transaction temperature.
• Comparisons in Tables.
• Provide Some photos and videos from industrial process.

Definition of polymerization.
Classification of polymerization and Compare between of these two types in terms
of:
Details, kind for everyone and kinetics as well as some examples of them and
Support your report with charts, images and videos as much as possible.
Please write about Autoacceleration, how can a void it in the industrial.

Your efforts will be appreciated.

Term paper should be more than 15 pages and submit it during B.B system at time.

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