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CHAPTER 4: What is a Polymer?

POLYMER STRUCTURES
Poly mer
ISSUES TO ADDRESS... many repeat unit
• What are the general structural and chemical
characteristics of polymer molecules? repeat repeat repeat
• What are some of the common polymeric unit unit unit
H H H H H H H H H H H H H H H H H H
materials, and how do they differ chemically?
C C C C C C C C C C C C C C C C C C
• How is the crystalline state in polymers different H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
from that in metals and ceramics ? Polyethylene (PE) Poly(vinyl chloride) (PVC) Polypropylene (PP)
Adapted from Fig. 4.2, Callister & Rethwisch 3e.

Chapter 4 - 1 Chapter 4 - 2

Ancient Polymers Polymer Composition

• Originally natural polymers were used Most polymers are hydrocarbons
– i.e., made up of H and C
– Wood – Rubber
• Saturated hydrocarbons
– Cotton – Wool – Each carbon singly bonded to four other atoms
– Leather – Silk – Example:
• Ethane, C2H6
• Oldest known uses
H
– Rubber balls used by Incas H H

– Noah used pitch (a natural polymer) C C

H
for the ark H H

Chapter 4 - 3 Chapter 4 - 4

Unsaturated Hydrocarbons
• Double & triple bonds somewhat unstable –
can form new bonds
– Double bond found in ethylene or ethene - C2H4
H H
C C
H H

– Triple bond found in acetylene or ethyne - C2H2

H C C H

Chapter 4 - 5 Chapter 4 - 6

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Polymerization and
Isomerism Polymer Chemistry
• Isomerism • Free radical polymerization
– two compounds with same chemical formula can H H H H
R + C C R C C initiation
have quite different structures
H H H H
for example: C8H18 free radical monomer
• normal-octane (ethylene)
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 H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
R C C + C C R C C C C propagation
H H H H H H H H
 H H H H H H H H
H3C ( CH2 ) CH3 dimer
6
• 2,4-dimethylhexane • Initiator: example - benzoyl peroxide
CH3
H3C CH CH2 CH CH3 H H H
CH2 C O O C 2 C O =2 R
CH3 H H H
Chapter 4 - 7 Chapter 4 - 8

Chemistry and Structure of

Bulk or Commodity Polymers
Polyethylene
Adapted from Fig.
4.1, Callister &
Rethwisch 3e.

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene
Chapter 4 - 9 Chapter 4 - 10

Bulk or Commodity Polymers (cont) Bulk or Commodity Polymers (cont)

Chapter 4 - 11 Chapter 4 - 12

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MOLECULAR WEIGHT Degree of Polymerization, DP

• Molecular weight, M: Mass of a mole of chains.
DP = average number of repeat units per chain

H H H H H H H H H H H H
Low M
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
high M DP =
m
Not all chains in a polymer are of the same length where m = average molecular weight of repeat unit
— i.e., there is a distribution of molecular weights for copolymers this is calculated as follows:
m = fi mi
Chapter 4 - 13
Chain fraction mol. wt of repeat unit i Chapter 4 - 14

Molecular Structures for Polymers 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
secondary
bonding to alter molecular shape

Linear Branched Cross-Linked Network Adapted from Fig.

4.5, Callister &
Adapted from Fig. 4.7, Callister & Rethwisch 3e. Rethwisch 3e.

Chapter 4 - 15 Chapter 4 - 16

Chain End-to-End Distance, r Molecular Configurations for Polymers

Configurations – to change must break bonds
• Stereoisomerism

H H H H H R
Adapted from Fig.
C C C C or C C
4.6, Callister & H R
Rethwisch 3e. 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 4 - 17 Chapter 4 - 18

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Tacticity Tacticity (cont.)

Tacticity – stereoregularity or spatial arrangement of R
units along chain atactic – R groups randomly
positioned
isotactic – all R groups on syndiotactic – R groups
same side of chain alternate sides H H H H H R H H
C C C C C C C C
H H H H H H H H H H H R H H H R
H R 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 4 - 19 Chapter 4 - 20

cis/trans Isomerism Copolymers Adapted from Fig.

4.9, Callister &
Rethwisch 3e.

two or more monomers random

polymerized together
CH3 H CH3 CH2
• random – A and B randomly
C C C C positioned along chain
CH2 CH2 CH2 H • alternating – A and B
alternate in polymer chain alternating

cis trans • block – large blocks of A

units alternate with large block
cis-isoprene trans-isoprene blocks of B units
(natural rubber) (gutta percha)
• graft – chains of B units
H atom and CH3 group on H atom and CH3 group on grafted onto A backbone
same side of chain opposite sides of chain

A– B–
graft
Chapter 4 - 21 Chapter 4 - 22