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Polymer Structures: Issues To Address..

This document summarizes key points about polymer structures and properties from Chapter 14. It discusses the general characteristics of polymer molecules, including their repeat unit structure and common materials like polyethylene, polypropylene, and poly(vinyl chloride). It also addresses crystalline structures in polymers, noting they differ from metals and ceramics. Molecular weight, tacticity, crystallinity and other structural features that influence polymer properties are summarized.

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JohnRenz Villegas
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51 views35 pages

Polymer Structures: Issues To Address..

This document summarizes key points about polymer structures and properties from Chapter 14. It discusses the general characteristics of polymer molecules, including their repeat unit structure and common materials like polyethylene, polypropylene, and poly(vinyl chloride). It also addresses crystalline structures in polymers, noting they differ from metals and ceramics. Molecular weight, tacticity, crystallinity and other structural features that influence polymer properties are summarized.

Uploaded by

JohnRenz Villegas
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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Chapter 14:

Polymer Structures
ISSUES TO ADDRESS...
What are the general structural and chemical
characteristics of polymer molecules?
What are some of the common polymeric
materials, and how do they differ chemically?
How is the crystalline state in polymers different
from that in metals and ceramics ?

Chapter
1 14 -

What is a Polymer?
Poly

mer
many

repeat unit

repeat
unit

repeat
unit

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

H H
C C
CH3 H

H H
C C
CH3 H

H
C
CH3

Polypropylene (PP)

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

Chapter
2 14 -

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
3 14 -

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

H
C
H

Chapter
4 14 -

Chapter
5 14 -

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

H
C C

H C C H
Chapter
6 14 -

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

CH3
2,4-dimethylhexane
H3C CH CH2 CH CH3
CH2
CH3
Chapter
7 14 -

Polymerization and
Polymer Chemistry
Free radical polymerization
R

H H

H H

C C

R C C

free radical

H H
monomer
(ethylene)

H H

H H

H H H H

C C

R C C C C

H H

H H H H

R C C
H H

initiation

H H

propagation

dimer

Initiator: example - benzoyl peroxide


H

C O O C
H

H
H

C O

= 2R

H
Chapter
8 14 -

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
9 14 -

Bulk or Commodity Polymers

Chapter
1014 -

Bulk or Commodity Polymers (cont)

Chapter
1114 -

Bulk or Commodity Polymers (cont)

Chapter
1214 -

VMSE: Polymer Repeat Unit Structures

Manipulate and rotate polymer structures in 3-dimensions


Chapter
1314 -

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
1414 -

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
1514 -

Molecular Weight Calculation


Example: average mass of a class
Student

Weight
mass (lb)

104

116

140

143

180

182

191

220

225

10

380

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?

Chapter
1614 -

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
range

number of
students
Ni

mass (lb)

81-120
121-160
161-200
201-240
241-280
281-320
321-360
361-400

2
2
3
2
0
0
0
1

total
number

Ni
10

mean
weight

number
Calculateweight
the number and weight
fraction
fraction
fraction of
students in each weight
Wi
xirange as follows:
wi
NiWi
Ni
mass (lb)
wi
xi
110
0.2
Ni
NiWi
0.117
142
0.2
0.150
184
0.3
0.294
For example:
for the 81-120 lb range
223
0.2
0.237

0
2
x811200.000

0.2
10
0
0.000
0
0.0002 x 110

0.117
380
0.1 w 81120
0.202

1881

NiWi
1881

total
weight

Chapter
1714 -

Molecular Weight Calculation (cont.)


weight
range

mean
weight

mass (lb)

Wi
mass (lb)

81-120
121-160
161-200
201-240
241-280
281-320
321-360
361-400

110
142
184
223
380

number
fraction
xi

weight
fraction
wi

0.2
0.2
0.3
0.2
0
0
0
0.1

0.117
0.150
0.294
0.237
0.000
0.000
0.000
0.202

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
M w wi Mi (0.117 x 110 0.150 x 142 + 0.294 x 184
M w wi Mi 218 lb

+ 0.237 x 223 + 0.202 x 380) = 218 lb


Chapter
1814 -

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
1914 -

Molecular Structures for Polymers

secondary

bonding

Linear

Branched

Cross-Linked

Network

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

Chapter
2014 -

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
2114 -

Chain End-to-End Distance, r

Adapted from Fig.


14.6, Callister &
Rethwisch 8e.

Chapter
2214 -

Molecular Configurations for Polymers


Configurations to change must break bonds
Stereoisomerism
H

H
C C

H H

H R
or

C C
R

Stereoisomers are mirror


images cant superimpose
without breaking a bond

C C

H R

H H

mirror
plane
Chapter
2314 -

Tacticity
Tacticity stereoregularity or spatial arrangement of R
units along chain
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

Chapter
2414 -

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

Chapter
2514 -

cis/trans Isomerism

CH3

H
C C

CH2

CH2

CH3

C C

CH2

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

Chapter
2614 -

VMSE: Stereo and Geometrical Isomers

Manipulate and rotate polymer structures in 3-dimensions


Chapter
27714- 19

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

Adapted from Fig.


14.9, Callister &
Rethwisch 8e.

random

alternating
block

graft
Chapter
2814 -

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
2914 -

Polymer Crystallinity
Crystalline regions
thin platelets with chain folds at faces
Chain folded structure
Adapted from Fig.
14.12, Callister &
Rethwisch 8e.

10 nm

Chapter
3014 -

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.)

Chapter
3114 -

Polymer Single Crystals


Electron micrograph multilayered single crystals
(chain-folded layers) of polyethylene
Single crystals only for slow and carefully controlled
growth rates

Adapted from Fig. 14.11, Callister & Rethwisch 8e.

Chapter
3214 -

Semicrystalline Polymers

Spherulite
surface

Some semicrystalline
polymers form
spherulite structures
Alternating chain-folded
crystallites and
amorphous regions
Spherulite structure for
relatively rapid growth
rates
Adapted from Fig. 14.13, Callister & Rethwisch 8e.

Chapter
3314 -

Photomicrograph Spherulites in
Polyethylene
Cross-polarized light used
-- a maltese cross appears in each spherulite

Adapted from Fig. 14.14, Callister & Rethwisch 8e.

Chapter
3414 -

ANNOUNCEMENTS
Reading:
Core Problems:
Self-help Problems:

Chapter
3514 -

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