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. 4.2, Callister & Rethwisch 3e.

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

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

3
 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

H C C H
Triple bond found in acetylene or ethyne - C2H2
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
6
 Polymerization and
Polymer Chemistry
Free radical polymerization
H H H H
R + C C R C C initiat ion
H H H H
free radical monomer
(ethylene)

H H H H H H H H
R C C + C C R C C C C propagation
H H H H H H H H
dimer
Initiator: example - benzoyl peroxide

H H H
C O O C 2 C O = 2R
H H H
7

Chemistry and Structure of

Polyethylene
Adapted from Fig.
4.1, Callister &
Rethwisch 3e.

Note: polyethylene is a long-chain hydrocarbon

- paraffin wax for candles is short polyethylene
8

Bulk or Commodity Polymers

9
 Bulk or Commodity Polymers (cont)

10

Bulk or Commodity Polymers (cont)

11

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

12
 MOLECULAR WEIGHT DISTRIBUTION
Adapted from Fig. 4.4, Callister & Rethwisch 3e.

totalwt of polymer


t ot al# of molecules

M n
xi M i
M w

w i M i

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
13

Molecular Weight Calculation

Example: average mass of a class
Student Weight
mass (lb) What is the average
1 104 weight of the students in
this class:
2 116
a) Based on the number
3 140
fraction of students in
4 143
each mass range?
5 180 b) Based on the weight
6 182 fraction of students in
7 191 each mass range?
8 220
9 225
10 380 14

Molecular Weight Calculation (cont.)

Solution: The first step is to sort the students into weight ranges.
Using 40 lb ranges gives the following table:
weight number of mean number
Calculate weight
the number and weight
range students weight fraction
fraction fraction
of students in each weight
Ni Wi xirange as follows:
wi
mass (lb) mass (lb) Ni N iWi
81-120 2 110 0.2 x i=  0.117
Ni
w i=
 N iW i
121-160 2 142 0.2 0.150
161-200 3 184 0.3For example:
0.294for the 81-120 lb range
201-240 2 223 0.2 0.237
2
241-280 0 - = =0,2
0 x 811200.000
10
281-320 0 - 0 0.000
321-360 0 - 0 0.0002110
w 81120 = =0,117
361-400 1 380 0.1 0.202 1881

N

i
N
iW
i total
total
number 10 1881 weight 15
 Molecular Weight Calculation (cont.)
weight mean number weight
range weight fract ion fract ion
Wi xi wi
mass (lb) mass (lb)
81-120 110 0.2 0.117
121-160 142 0.2 0.150
161-200 184 0.3 0.294
201-240 223 0.2 0.237
241-280 - 0 0.000
281-320 - 0 0.000
321-360 - 0 0.000
361-400 380 0.1 0.202

M n = x i M i= 0,21100,21420,31840,22230,1380  =188 lb

M w =  w i M i= 0,1171100,1501420,2941840,2372230,202380 =218 lb

M w = wi M i=218 lb
16

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=
f i m i

Chain fraction mol. wt of repeat unit i 17

Molecular Structures for Polymers

secondary
bonding

Linear Branched Cross-Linked Network

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

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 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.

4.5, Callister &
Rethwisch 3e.

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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 cant superimpose C C
without breaking a bond E E
B D D B
mirror
plane
20

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

21
 Tacticity (cont.)
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

22

cis/trans Isomerism

CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H

cis trans
cis-isoprene trans-isoprene
(natural rubber) (gutta percha)
H atom and CH3 group on H atom and CH3 group on
same side of chain opposite sides of chain

23

Copolymers Adapted from Fig.

4.9, Callister &
Rethwisch 3e.

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
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 Crystallinity in Polymers Adapted from Fig.
4.10, Callister &
Rethwisch 3e.
Ordered atomic
arrangements involving
molecular chains
Crystal structures in terms
of unit cells
Example shown
polyethylene unit cell

25

Polymer Crystallinity
Crystalline regions
thin platelets with chain folds at faces
Chain folded structure

Adapted from Fig.

4.12, Callister &
Rethwisch 3e.

10 nm

26

Polymer Crystallinity (cont.)

Polymers rarely 100% crystalline
Difficult for all regions of all chains to
become aligned crystalline
region
Degree of crystallinity
expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase.
amorphous
region
Adapted from Fig. 14.11, Callister 6e.
(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of
Materials, Vol. III, Mechanical Behavior, John Wiley
and Sons, Inc., 1965.) 27
Semicrystalline Polymers
Some semicrystalline
polymers form
spherulite structures
Alternating chain-folder
crystallites and
amorphous regions
Spherulite structure for
relatively rapid growth
Spherulite rates
surface

Adapted from Fig. 4.13, Callister & Rethwisch 3e.

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