Polymer Lecture Notes

Gary E. Wnek and Anthony Guiseppi-Elie

sp
3
Hybridized Carbon
Tetrahedron


Simplest structure for an sp3 hybridized carbon
Methane










Linear Polymer




Branched Polymer




Network






More complex polymer architectures: combs, stars, rigid rods,
dendrimers.....








3-Arm Star Polymer
Comb Polymer

----------------------------------------------------------------------
Thermoplastic polymer that will melt and flow (can be re-
shaped)
Thermoset polymer that cannot melt or flow due to covalent
bonding between chains
Isomerism in Polymers

1. Structural Isomerism



2. Stereoisomerism



CH
2
CHCH
2
CHCH
2
CHCH
2
CH
R R R R
CH
2
CHCHCH
2
CH
2
CHCHCH
2
R R R R
'head-to-tail'
'head-to-head'
CH
2
C C
CH
2
H H
3
C
CH
2
C C
CH
2
H
H
3
C
cis-1,4-polyisoprene trans-1,4-polyisoprene

Molecular Weight of Polymers



Number-Average Molecular Weight (M
n
)
M
n
= N
i
M
i
/
N
i

where

N
i
is the number of molecules of ith species of molecular
weight M
i
.

Measured from colligative properties (freezing point depression for
low molecular weight, osmotic pressure for higher molecular
weight; gel permeation or size exclusion chromatography)

Weight-Average Molecular Weight (M
W
)
M
W
= N
i
M
i
2
/
N
i
M
i

Biases higher molecular weight chains. Measured using light
scattering (scattered intensity is proportional to square of
R R R
Isotactic
R R
R
Syndiotactic
R R
R
Heterotactic or
Atactic (random)
polarizability; polarizability proportional to mass); gel permeation
or size exclusion chromatography)
Polydispersity = M
W
/
M
n


Polymer sample containing 95wt% of 10,000 g/mol + 5wt% of 100
g/mol: M
W
= 9505 g/mol; M
n
= 1680 g/mol;M
W/
M
n
= 5.66

Properties (e.g., the melting point, T
m
) of
collections of small organic molecules depend on:

Molecular weight

Molecular symmetry

Conformational flexibility

Strength of intermolecular forces

From thermodynamics:
G = H - TS

At the melting point, T = T
m
and G
m
= 0.
Therefore:
T
m
= H
m
/S
m


T
m
and H
m
are readily measured by calorimetry,
allowing calculation of S
m
.

n-pentane, n-hexane
















Crystal Melt
Many conformations available in the melt; S
m
is high

S = k ln
Isomers of C
5
H
12










n-pentane






2-methylbutane (isobutane)








2,2-dimethylpropane (neopentane)







n-octane









Benzoic acid Anthracene


Compound T
m
,K H
m
, kJ/mol S
m
, J/mol-K

pentane 143 8.37 58.58
2-methyl- 113 5.10 43.10
butane
neopentane 256 3.22 12.97
n-octane 217 20.50 94.14
n-pentacosane 326 77.40 237.65
(C
25
H
52
)
benzoic acid 395 17.57 44.35
anthracene 490 28.8 58.7









Compound T
m
, K
H
m
, kJ/mol S
m
, J/mol-K
Pentane
(C
5
H
12
)
143 8.37 58.58
n-octane
(C
8
H
18
)
217 20.50 94.14
n-pentacosane
(C
25
H
52
)
326 77.40 237.65
Polyethylene
(CH
2
)
n



-250
-200
-150
-100
-50
0
50
1 3 5 7 9 11 13 15
M
e
l
t
i
n
g

P
o
i
n
t

(
o
C
)

Number of Carbon Atoms
Melting Points of Normal Alkanes


Glasses

Glass: substance with the structural characteristics of a
liquid and mechanical characteristics of a solid.


Tendency to form a glass after bypassing T
m
is increased if:


Cooling rates are high

The viscosity of the melt is high

The constituents (molecules) are complex

The temperature at which a supercooled liquid (liquid below
T
m
) becomes a glass, or vitrifies, is termed the glass
transition temperature, T
g
. At T
g
large-scale molecular
motion effectively ceases.
Some small organic molecules are able to form glasses:

Compound T
m
, K T
g
, K T
g
/T
m

V*
Pentane 143 - -

2-methylpentane 119 80 0.67

methylcyclohexane 146 85 0.58

toluene 178 112 0.63

2-butanol 298 152 0.34

i-butyl chloride 142 37 0.26

























Volume changes accompanying the formation of crystals or
a glass upon cooling from the melt



Large, organic polymeric molecules are able to form
glasses:

Supercooled Stable
liquid liquid



Glass Transition Range




Formation
of Crystals
Fast
cooling



Slow cooling




Volume, V
Temperature, T
T
g
range
T
m

Polymer T
m
, K T
g
, K T
g
/T
m

V*
PDMS
polydimethylsiloxane
silicone
48 132
PIB
polyisobutylene
rubber
203 127
cis-p-isoprene
rubber
203 252
PVAc
poly(vinylacetate)
glue
300 341
PVC
poly(vinylchloride)
pipe
343 508
PS
polystyrene
packaging plastic
373 836
PMMA
polymethylmethacrylate
plexiglas
378 1427
PPO
polyphenlyene oxide
High performance plastic
498 1980










Polymer T
g
, C(F) T
m
, C(F) T
m
/T
g
T
m
-T
g

Polyethylene LDPE -110 (-165) 115 (240) -1.05 225
Polytetrafluoroethylene -97 (-140) 327 (620) -3.37 424
Polyethylene HDPE -90 (-130) 137 (279) -1.52 227
Polypropylene -18 (0) 175 (347) -9.72 193
Nylon 6,6 57 (135) 265 (510) 4.65 208
Polyester 69 (155) 265 (510) 3.84 196
Polyvinyl chloride 87 (190) 212 (415) 2.44 125
Polystyrene 100 (212) 240 (465) 2.40 140
Polycarbonate 150 (300) 265 (510) 1.77 115






Liquid Crystals







Nematic Smectic A Smectic C



















Cholesteric
Molecules that form liquid crystal phases are called
mesogens. They are usually conformationally
inflexible.


Examples:





nematic (liquid crystal range ca. 14-28
o
C)








smectic A (liquid crystal range ca. 121-131
o
C)



cholesteric (liquid crystal range ca. 53-97
o
C)




Solubility

Like dissolves like similar intermolecular forces

However, entropic considerations are also important
Consider benzene (X) and carbon tetrachloride (O)


CH
3
C
H
3
C
CH
3
CH
3
CH
3
O
O H
3
C(CH
2
)
7







There are many permutations!

S = k ln


Solubility in the absence of mutually strong intermolecular
forces is typically driven by entropy



Prediction of Solubility via
Solubility Parameters

For 2 non-polar liquids, where H
mix
is > 0:

H
mix
= [(E
1
/V
1
)
1/2
- [(E
2
/V
2
)
1/2
]
2
V
1

2


X X
X
X
X
X
X
O O
O O
O O
O O X
(Scatchard-Hildebrand Eq.)

where E
1
and E
2
are the energies of vaporization of
components 1 and 2 which have molar volumes V
1
and V
2
,
and
1
and
2
are their volume fractions.

(E
1
/V
1
)
1/2
and (E
2
/V
2
)
1/2
are solubility parameters
(s)

Solvent , (cal/cm
3
)
1/2
n-hexane 7.2
toluene 8.9
THF 9.1
MEK 9.3
acetone 9.9
methanol 14.5
water 23.4