Chapter 14:

Polymer Structures

‫سليمان يونس سليمان سعد‬

213257

Chapter 14 - 1
 What is a Polymer?

Poly mer
many repeat unit

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)
Adapted from Fig. 14.2, Callister & Rethwisch 8e.

Chapter 14 - 2
 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

Chapter 14 - 3
 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
H
C C

H H
H

Chapter 14 - 4
Chapter 14 - 5
 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
Chapter 14 - 6
 Chemistry and Structure of
Polyethylene
Adapted from Fig.
14.1, Callister &
Rethwisch 8e.

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene
Chapter 14 - 7
Bulk or Commodity Polymers

Chapter 14 - 8
Bulk or Commodity Polymers (cont)

Chapter 14 - 9
Bulk or Commodity Polymers (cont)

Chapter 14 -10
 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

Chapter 14 - 11
 MOLECULAR WEIGHT DISTRIBUTION
Adapted from Fig. 14.4, Callister & Rethwisch 8e.

total wt of polymer
Mn =
total # of molecules

M n = xi Mi
M w = wi Mi

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
Chapter 14 -12
 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

Mn
DP =
m

where m = average molecular weight of repeat unit

for copolymers this is calculated as follows:
m = fi mi
Chain fraction mol. wt of repeat unit i Chapter 14 -13
Molecular Structures for Polymers

secondary
bonding

Linear Branched Cross-Linked Network

Adapted from Fig. 14.7, Callister & Rethwisch 8e.

Chapter 14 -14
 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 8e.

Chapter 14 -15
Chain End-to-End Distance, r

Adapted from Fig.

14.6, Callister &
Rethwisch 8e.

Chapter 14 -16
 Molecular Configurations for Polymers
Configurations – to change must break bonds
• Stereoisomerism

H H H H H R
C C C C or C C
H R
H R H H

A A
Stereoisomers are mirror
images – can’t superimpose C C
without breaking a bond E E
B D D B
mirror
plane

Chapter 14 -17
 Tacticity
Tacticity – stereoregularity or spatial arrangement of R
units along chain

isotactic – all R groups on syndiotactic – R groups

same side of chain 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

Chapter 14 -18
 Copolymers Adapted from Fig.
14.9, Callister &
Rethwisch 8e.

two or more monomers random

polymerized together
• random – A and B randomly
positioned along chain
• alternating – A and B
alternate in polymer chain alternating
• block – large blocks of A
units alternate with large block
blocks of B units
• graft – chains of B units
grafted onto A backbone

A– B–
graft
Chapter 14 -19
 Crystallinity in Polymers Adapted from Fig.
14.10, Callister &
Rethwisch 8e.
• Ordered atomic
arrangements involving
molecular chains
• Crystal structures in terms
of unit cells
• Example shown
– polyethylene unit cell

Chapter 14 -20