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Chapter 14: 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. 14.2, Callister & Rethwisch 8e.
Chapter 14 - 1 Chapter 14 - 2
1 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
– Rubber balls used by Incas H
H H
– Noah used pitch (a natural polymer) C C
H
for the ark H H
Chapter 14 - 3 Chapter 14 - 4
3 4
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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 14 - 5 Chapter 14 - 6
5 6
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 =2R
CH3 H H H
Chapter 14 - 7 Chapter 14 - 8
7 8
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Chemistry and Structure of
Bulk or Commodity Polymers
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 - 9 Chapter 14 -10
9 10
Bulk or Commodity Polymers (cont) Bulk or Commodity Polymers (cont)
Chapter 14 - 11 Chapter 14 -12
11 12
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VMSE: Polymer Repeat Unit Structures 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
Manipulate and rotate polymer structures in 3-dimensions
Chapter 14 - 13 Chapter 14 -14
13 14
MOLECULAR WEIGHT DISTRIBUTION Molecular Weight Calculation
Adapted from Fig. 14.4, Callister & Rethwisch 8e.
total wt of polymer Example: average mass of a class
Mn =
total # of molecules
Student Weight
mass (lb) What is the average
M n = xi Mi 1 104 weight of the students in
this class:
2 116
M w = wi Mi 3 140
a) Based on the number
fraction of students in
4 143
each mass range?
5 180 b) Based on the weight
6 182 fraction of students in
Mi = mean (middle) molecular weight of size range i 7 191 each mass range?
xi = number fraction of chains in size range i 8 220
wi = weight fraction of chains in size range i 9 225
Chapter 14 -15 10 380 Chapter 14 -16
15 16
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Molecular Weight Calculation (cont.) Molecular Weight Calculation (cont.)
weight mean number weight
Solution: The first step is to sort the students into weight ranges.
range weight fraction fraction
Using 40 lb ranges gives the following table:
Wi xi wi
weight number of mean numberCalculateweight
the number and weight mass (lb) mass (lb)
range students weight fraction fraction
fraction of students in each weight 81-120 110 0.2 0.117
Ni Wi xirange as follows:
wi 121-160 142 0.2 0.150
mass (lb) mass (lb) Ni NiWi 161-200 184 0.3 0.294
xi = wi =
81-120 2 110 0.2 0.117
Ni NiWi 201-240 223 0.2 0.237
121-160 2 142 0.2 0.150 241-280 - 0 0.000
161-200 3 184 0.3 0.294 281-320 - 0 0.000
For example: for the 81-120 lb range
201-240 2 223 0.2 0.237 321-360 - 0 0.000
2
241-280 0 - 0 x =
0.000
81−120 = 0.2 361-400 380 0.1 0.202
281-320 0 - 0 0.000 10 M n = xi Mi = (0.2 x 110 + 0.2 x 142 + 0.3 x 184 + 0.2 x 223 + 0.1 x 380) = 188 lb
321-360 0 - 0 0.0002 x 110
361-400 1 380 0.1 w 81−120 0.202= = 0.117 M w = wi Mi = (0.117 x 110 + 0.150 x 142 + 0.294 x 184
1881
+ 0.237 x 223 + 0.202 x 380) = 218 lb
total Ni NiWi total M w = wi Mi = 218 lb
number 10 1881 weight Chapter 14 -17 Chapter 14 -18
17 18
Degree of Polymerization, DP Molecular Structures for Polymers
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 secondary
bonding
Mn
DP = Linear Branched Cross-Linked Network
m
Adapted from Fig. 14.7, Callister & Rethwisch 8e.
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 -19 Chapter 14 -20
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Polymers – Molecular Shape Chain End-to-End Distance, r
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
Adapted from Fig.
to alter molecular shape 14.6, Callister &
Rethwisch 8e.
Adapted from Fig.
14.5, Callister &
Rethwisch 8e.
Chapter 14 -21 Chapter 14 -22
21 22
Molecular Configurations for Polymers Tacticity
Configurations – to change must break bonds
Tacticity – stereoregularity or spatial arrangement of R
units along chain
• Stereoisomerism
isotactic – all R groups on syndiotactic – R groups
H H H H H R same side of chain alternate sides
C C C C or C C
H R H H H H H H H H H H H R H H H R
H R H H
C C C C C C C C C C C C C C C C
A A
Stereoisomers are mirror H R H R H R H R H R H H H R H H
images – can’t superimpose C C
without breaking a bond E E
B D D B
mirror
plane
Chapter 14 -23 Chapter 14 -24
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Tacticity (cont.) cis/trans Isomerism
atactic – R groups randomly
positioned
CH3 H CH3 CH2
H H H H H R H H C C C C
CH2 CH2 CH2 H
C C C C C C C C
H R H R H H H R 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
Chapter 14 -25 Chapter 14 -26
25 26
VMSE: Stereo and Geometrical Isomers 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–
Manipulate and rotate polymer structures in 3-dimensions graft
Chapter 714- -19
27 Chapter 14 -28
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Crystallinity in Polymers Adapted from Fig. Polymer Crystallinity
14.10, Callister &
Rethwisch 8e.
• Ordered atomic • Crystalline regions
arrangements involving – thin platelets with chain folds at faces
molecular chains – Chain folded structure
• Crystal structures in terms
of unit cells Adapted from Fig.
14.12, Callister &
• Example shown Rethwisch 8e.
10 nm
– polyethylene unit cell
Chapter 14 -29 Chapter 14 -30
29 30
Polymer Crystallinity (cont.) Polymer Single Crystals
Polymers rarely 100% crystalline • Electron micrograph – multilayered single crystals
• Difficult for all regions of all chains to (chain-folded layers) of polyethylene
become aligned crystalline • Single crystals – only for slow and carefully controlled
region
growth rates
• 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 Adapted from Fig. 14.11, Callister & Rethwisch 8e.
and Sons, Inc., 1965.) Chapter 14 -31 Chapter 14 -32
31 32
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Photomicrograph – Spherulites in
Semicrystalline Polymers Polyethylene
• Some semicrystalline Cross-polarized light used
polymers form -- a maltese cross appears in each spherulite
spherulite structures
• Alternating chain-folded
crystallites and
amorphous regions
• Spherulite structure for
relatively rapid growth
Spherulite rates
surface
Adapted from Fig. 14.13, Callister & Rethwisch 8e.
Chapter 14 -33 Adapted from Fig. 14.14, Callister & Rethwisch 8e. Chapter 14 -34
33 34
ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:
Chapter 14 -35
35
