Lecture 17.

Polymer Structures
Learning Objectives

After this lecture, you should be able to do the following:

1. Describe a polymer molecule in terms of its chain structure and how

the molecule may be generated from repeat units
2. Calculate molecule weights and degree of polymerization.
3. Describe types of polymer molecular structures and isomers.

Reading

Chapter 14: Polymer Structures (14.114.11)

Multimedia

Virtual Materials Science & Engineering (VMSE):

http://www.wiley.com/college/callister/CL_EWSTU01031_S/vmse/
Polyethylene Terephthalate Polymerization:
https://www.youtube.com/watch?v=Pnbfv7WJkOk

MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 1

1. What is a Polymer?

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Lecture 17 - 2

What is a Polymer?
Poly
many

repeat
unit

mer
repeat unit
(part)

repeat
unit

H H H H H H
C C C C C C
H H H H H H

H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Poly(vinyl chloride) (PVC)

H
C
H

repeat
unit

H H
C C
CH3 H

H H
C C
CH3 H

H
C
CH3

Polypropylene (PP)

A repeat unit is also sometimes called a mer. Mer originates from the Greek word
meros, which means part; the term polymer was coined to mean many mers.
MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 3

Ancient Polymers
Originally natural polymers were used
Wood
Rubber
Cotton
Wool
Leather
Silk
Oldest known uses
Rubber balls used by Incas
Noah used pitch (a natural polymer)
for the ark
MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 4

Polymer Composition
Most polymers are hydrocarbons
i.e., made up of H and C
Saturated hydrocarbons
Each carbon singly bonded to four other atoms
Example:
Ethane, C2H6
H

H
C

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H
C
H

Lecture 17 - 5

Unsaturated Hydrocarbons
Double & triple bonds somewhat unstable
can form new bonds

Double bond found in ethylene or ethene - C2H4

H
C C

Triple bond found in acetylene or ethyne - C2H2

H C C H
MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 6

Covalent Bonding

similar electronegativity share electrons

bonds determined by valence s & p orbitals dominate bonding
Example: H2
H2
Each H: has 1 valence e-,
needs 1 more
Electronegativities
are the same.

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shared 1s electron
from 1st hydrogen
atom

shared 1s electron
from 2nd hydrogen
atom

Lecture 17 - 7

Bond Hybridization (sp3)

Carbon can form sp3 hybrid
orbitals

Fig. 2.14, Callister & Rethwisch 9e.

(Adapted from J.E. Brady and F. Senese, Chemistry:

Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

Fig. 2.13, Callister & Rethwisch 9e.

MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 8

Covalent Bonding: Carbon sp3

Example: CH4
C: has 4 valence e-,
needs 4 more
H: has 1 valence e-,
needs 1 more

Electronegativities of C and H
are comparable so electrons
are shared in covalent bonds.

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Fig. 2.15, Callister & Rethwisch 9e.

(Adapted from J.E. Brady and F. Senese, Chemistry:

Matter and Its Changes, 4th edition. Reprinted with
permission of John Wiley and Sons, Inc.)

Lecture 17 - 9

Reviews: Hydrocarbons

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Lecture 17 - 10

Reviews: Hydrocarbons

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Lecture 17 - 11

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Lecture 17 - 12

Isomerism
Isomerism
two compounds with same chemical formula can
have quite different structures
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

6

2,4-dimethylhexane
CH3

H3C CH CH2 CH CH3

CH2
CH3
MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 13

Polymerization and Polymer Chemistry

Free radical polymerization (polyethylene)
R

H H

C C

R C C

H H
monomer
(ethylene)

free radical
H H
R C C

H H

H H

initiation

H H

H H

H H H H

C C

R C C C C

H H

H H H H

propagation
propagation

dimer

Initiator (catalyst species): example - benzoyl

peroxide
H

C O O C
H
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H
H

C O

=2R

H
Lecture 17 - 14

Chemistry and Structure of

Polyethylene
Adapted from Fig.
14.1, Callister &
Rethwisch 9e.

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene
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Lecture 17 - 15

Bulk or Commodity Polymers

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Lecture 17 - 16

Bulk or Commodity Polymers (cont)

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Lecture 17 - 17

Bulk or Commodity Polymers (cont)

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Lecture 17 - 18

VMSE: Polymer Repeat Unit Structures

Manipulate and rotate polymer structures in 3-dimensions

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Lecture 17 - 19

2. MOLECULAR WEIGHT
Molecular weight, M: Mass of a mole of chains.

Low M

high M

Not all chains in a polymer are of the same length

i.e., there is a distribution of molecular weights

MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 20

MOLECULAR WEIGHT DISTRIBUTION

Fig. 14.4, Callister & Rethwisch 9e.

Mi = mean (middle) molecular weight of size range i

xi = number fraction of chains in size range i
wi = weight fraction of chains in size range i
MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 21

Molecular Weight Calculation

Example: average mass of a class
Student

Weight
mass (lb)

104

116

140

143

180

182

191

220

225

10

380

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What is the average

weight of the students in
this class:
a) Based on the number
fraction of students in
each mass range?
b) Based on the weight
fraction of students in
each mass range?

Lecture 17 - 22

Molecular Weight Calculation (cont.)

Solution: The first step is to sort the students into weight ranges.
Using 40 lb ranges gives the following table:

Calculate the number and weight

fraction of students in each weight
range as follows:

For example: for the 81-120 lb range

total
number

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total
weight

Lecture 17 - 23

Molecular Weight Calculation (cont.)

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Lecture 17 - 24

Degree of Polymerization, DP
DP = average number of repeat units per chain
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 H

DP = 6

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

Chain fraction

MSE 3300 / 5300 UTA Spring 2015

mol. wt of repeat unit i

Lecture 17 - 25

Molecular Structures for Polymers

secondary

bonding

Linear

B ranched

Cross-Linked

Network

Adapted from Fig. 14.7, Callister & Rethwisch 9e.

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Lecture 17 - 26

Polymers Molecular Shape

Molecular Shape (or Conformation) chain
bending and twisting are possible by rotation
of carbon atoms around their chain bonds
note: not necessary to break chain bonds
to alter molecular shape
Adapted from Fig.
14.5, Callister &
Rethwisch 9e.

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Lecture 17 - 27

Chain End-to-End Distance, r

Fig. 14.6, Callister &

Rethwisch 9e.

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Lecture 17 - 28

Molecular Configurations:
(1) Stereoisomerism
Stereoisomerism
isotactic all R groups on
same side of chain

syndiotactic R groups
alternate sides

H H H H H H H H

H H H R H H H R

C C C C C C C C

C C C C C C C C

H R H R H R H R

H R H H H R H H

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Lecture 17 - 29

Molecular Configurations:
(1) Stereoisomerism
isotactic all R groups on
same side of chain

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syndiotactic R groups
alternate sides

Lecture 17 - 30

Molecular Configurations:
(1) Stereoisomerism
atactic R groups randomly
positioned
H H H H H R H H
C C C C C C C C
H R H R H H H R

MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 31

Molecular Configurations:
(2) Geometrical Isomerism
cis/trans Isomerism
CH3
CH2

C C

CH3

CH2

CH2

C C

CH2
H

cis

trans

cis-isoprene
(natural rubber)

trans-isoprene
(gutta percha)

H atom and CH3 group on

same side of chain

H atom and CH3 group on

opposite sides of chain

MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 32

Molecular Configurations for Polymers

Configurations to change must break bonds
Stereoisomerism
H
H

C C

H
R

Stereoisomers are mirror

images cant superimpose
without breaking a bond

H R

H H
or

C C

C C
H H

H R

E
D

mirror
plane
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Lecture 17 - 33

VMSE: Stereo and Geometrical Isomers

Manipulate and rotate polymer structures in 3-dimensions

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Lecture 17 - 34

Copolymers
two or more monomers
polymerized together
random A and B randomly
positioned along chain
alternating A and B
alternate in polymer chain
block large blocks of A
units alternate with large
blocks of B units
graft chains of B units
grafted onto A backbone
A
MSE 3300 / 5300 UTA Spring 2015

Fig. 14.9, Callister &

Rethwisch 9e.

random

alternating
block

graft
Lecture 17 - 35

Summary
1. What is a Polymer?
2. Chemistry of polymer molecules
3. Molecular weight (MW): number-averaged and
weight-averaged MW
4. Molecular structures: linear polymers, branched
polymers, crosslinked polymers, network polymers
5. Molecular configuration: stereoisomerism,
geometrical isomerism

MSE 3300 / 5300 UTA Spring 2015

Lecture 17 - 36