10/24/2016

CHM 3102
Polymer Chemistry

Topics
1. Introduction
2. Polymer synthesis
3. Copolymerization
4. Polymer solutions
5. Determination of Molecular Weight
6. Glass Transition
7. Thermal Analysis
8. Rubber Elasticity
9. Viscoelasticity
2

Main topics for Polymer solution

Learning Outcomes

How polymers dissolve: polymer dissolution

Flory-Huggins theory
The solubility parameter

At the end of this topic you are able to

describe the process of polymer dissolution

discuss the Flory-Huggins theory, assumptions
and limitation
explain the importance and use of the
solubility parameter

Polymer solutions
What

Why

Polymer Solutions: Introduction

are polymer solutions?

the need for us to discuss polymer

solutions?

Why

do we need to
know about polymer
solutions?

10/24/2016

The

reasons are based on the key factors:

The understanding of the behaviour and
both physical and chemical properties of
macromolecules has been mainly sustained
in studies carried out in solution.
For example the determination of the
relative molecular mass by viscometry,
colligative properties, or gel permeation
chromatography (GPC).
7

On

the other hand, since polymer

solutions are highly viscous even at low
concentrations, their commercial
application includes a wide range of
products, from shampoos to processed
foods.

What is a solution ?
Before

discussing these or other polymer

characterization techniques, we will
discuss the process of polymer
dissolution and thermodynamics of
polymer solutions.

A special type of Mixture

Single phase
More than one distinguishable chemical constituent
present
Homogeneous
Examples
solid solutions
liquid solutions

-----

alloys
syrup

10

Polymer Solubility
Not

all polymers can be dissolved, and

even though when they can, the
dissolution process may take up to
several days or weeks.
There is an assembly of general rules for
polymer solubility, based on experimental
observations, from which interesting
conclusions can be obtained.

the

dissolution of polymers depends not

only on their physical properties, but also
on their chemical structure, such as:
polarity, molecular weight, branching,
crosslinking degree, and crystallinity.
The general principle that states like
dissolves like is also appropriate in the case
of polymers.

10/24/2016

Polar

macromolecules like poly (acrylic

acid), poly (acrylamide) and polyvinyl
alcohol, among others, are soluble in
water.
Conversely, non-polar polymers or
polymer showing a low polarity such as
polystyrene, poly(methyl methacrylate)
and poly(vinyl chloride) are soluble in
non-polar solvents.

similar situation occurs with crystalline

macromolecules, although in such a case
the dissolution can be forced if an
appropriate solvent is available, or
warming the polymer up to temperatures
slightly below its crystalline melting point
(Tm).

The molecular weight of polymers plays an

important role in their solubility. In a given
solvent at a particular temperature, as
molecular weight increases, the solubility of a
polymer decreases.
This same behavior is also noticed as
crosslinking degree increases, since strongly
crosslinked polymers inhibit the interaction
between polymer chains and solvent
molecules, preventing those polymer chains
from being transported into solution.

For example, highly crystalline linear

polyethylene (Tm = 135C) can be dissolved in
several solvents above 100C.
Nylon 6,6 (Tm = 265C), a crystalline polymer
which is more polar than polyethylene, can be
dissolved at room temperature in the presence
of solvents with enough ability to interact with
its chains, through for example, hydrogen
bonding.

16

How a Polymer Gets Dissolved

Branched polymer chains generally increase
solubility, although the rate at which this
solubility occurs, depends on the particular
type of branching.
Chains containing long branches, cause dense
entanglements making difficult the penetration
of solvent molecules.
Therefore the rate of dissolution in these
cases becomes slower than if it was short
branching, where the interaction between
chains is practically non-existent.

As

mentioned earlier, the dissolution of a

polymer is generally a slow process,
depending on the structure and the
molecular weight of a given polymer.

10/24/2016

Something familiar..
When a low molecular weight solute
such as sucrose is added to water, the
dissolution process takes place
immediately.
The sugar molecules leave the crystal
lattice progressively, disperse in water, and
form a solution.

What

Polymer

Figure 1: Polymer dissolution processes

molecules constitute long chains

with a large number of segments, forming
tightly folded coils which are even
entangled to each other.
Numerous cohesive and attractive both
intra and intermolecular forces hold
these coils together, such a dispersion,
dipole-dipole interaction, induction, and
hydrogen bonding.

(a) Polymer molecules in solid state

just after being added to a solvent

(b) First step: A swollen gel in solvent

(c) Second step: Solvated polymer

molecules dispersed into a solution

happens when a solid polymer is

introduced to a liquid?

Based on these features, one may expect

noticeable differences in the dissolution
behavior shown by polymers.
Due to their size, coiled shape, and the
attraction forces between them, polymer
molecules become dissolved quite slowly
than low molecular weight molecules.
There are two stages involved in this process:
in the first place, the polymer swelling, and
next the dissolution step itself.

When a polymer is added to a given solvent,

attraction as well as dispersion forces begin
acting between its segments, according to their
polarity, chemical characteristics, and solubility
parameter.
If the polymer-solvent interactions are higher
than the polymer-polymer attraction forces,
the chain segment start to absorb solvent
molecules, increasing the volume of the
polymer matrix, and loosening out from their
coiled shape (Figure 1b).
The segments are now "solvated" instead of
"aggregated", as they were in the solid state.

10/24/2016

The

whole "solvation-unfolding-swelling"
process takes a long time, and given it is
influenced only by the polymer-solvent
interactions, stirring plays no role in this
case.
However, it is desirable to start with fine
powdered material, in order to expose
more of their area for polymer-solvent
interactions.

When

If the polymer-solvent interactions are still

strongly enough, the "solvation-unfoldingswelling" process will continue until all
segments are solvated.
The whole loosen coil will diffuse out of the
swollen polymer, dispersing into a solution.
At this stage, the disintegration of the swollen
mass can be favored by stirring, which
increases the rate of dissolution.

However, once

Hence, the

The

polymer coil, along with

solvent molecules held within, adopts a
spheric or ellipsoid form, occupying a
volume known as hydrodynamic volume of
the polymer coil (Figure 1c).

crystalline, hydrogen bonded or

highly crosslinked substances are involved,
where polymer-polymer interactions are
strong enough, the process does stop at
this first stage, giving a swollen gel as a
result.

all the chain segments

have been dispersed in the solvent phase,
they still retain their coiled conformation,
yet they are now unfolded, fully solvated,
and with solvent molecules filling the
empty space between the loosen
segments.

particular behavior shown by

polymer molecules, explains the high
viscosity of polymer solutions.
Solvent and low molecular weight solutes
have comparable molecular size, and the
solute does not swell when dissolving.

10/24/2016

Solubility Factors
Since molecular mobility is not restricted, and
therefore intermolecular friction does not
increase drastically, the viscosity of the solvent
and the solution are similar.
But the molecular size of polymer solutes is
much bigger than that of the solvent.
In the dissolution process such molecules swell
appreciably, restricting their mobility, and
consequently the intermolecular friction
increases. The solution in these cases, becomes
highly viscous.

Rate

of dissolution decreases with:-

Increasing

molecular weight
Increasing degree of crystillinity
Increasing number of crosslinking

Why do things dissolve?

Thermodynamics of dissolution
How do things dissolve?
Microscopic details of dissolution

33

H. Shirota & E. W. Castner, Jr., J.Chem.

Phys. 2006, 125, 034904.

34

Solution Thermodynamics
Solutions are often characterized in terms
of Gibbs free energy G.
G can be viewed as a multivariable
function that depends on temperature (T),
pressure (P), and the number of moles of
each component (ni for i = 1 to number of
components).
35

By multivariable math analysis, the

differential in free energy following a
change in any or all of the key
variables is:

36

10/24/2016

The subscripts on the partial

derivatives mean that those variables
are held constant while taking
the derivative.

37

By using lower case n to mean

moles of some component and
upper case N to mean molecules,
the number of molecules N is
always equal to nL where L is
Avagadros number.

38

The terms in the dG expression from

conventional thermodynamics.

The differential in free energy follows the

well known relation

Consider a solution with constant

composition (i.e., dni = 0 for all i ).

dG = V dP - SdT

The total free energy is

G = H - TS
39

40

dG = V dP - SdT

Comparing this expression to the solution

results above gives

Hmix for an ideal solution is zero.

free energy of mixing can be split up into an entropy

part and an enthalpy part with

41

Hmix is zero because the assumption

of an ideal solution implies no
interactions between the components of
the solution.
42

10/24/2016

From,

These facts mean that Gmix is always

negative and Smix is always positive.

Examine the sign of Gmix.

In other words all two component ideal

solutions are miscible in all proportions.

Both nA and nB, the numbers of moles, must be

positive. Both XA and XB, the mole fractions,
must between 0 and 1, which means that both
lnXA and lnXB must be negative.

The driving force for this miscibility is the

increase in entropy of mixed components
vs. pure separated components.

43

44

Molecular theory of polymer solution: Lattice Model (F.1)

To make two components immiscible,

Gmix must be positive which implies
that
Hmix 0

1
Solvent molecule
Low molecular weight molecule

F .1: A simple lattice model for a solution of A and B.

and further that Hmix is sufficiently

positive that it overwhelms the entropy
or that
Hmix > TSmix.
45

Solvent molecule

Polymer molcule
with x segmens

46

F 2: Polymer molecule B in a lattice model for a solution in solvent A.

Molecular theory of polymer solution: Lattice Model (F.1)

Origins of Entropy of Mixing

A
Solvent molecule
Low molecular weight molecule

Solvent molecule

Physical origins of the entropy of mixing can be

modeled using a simple lattice model for the
structure of a solution.
Say the simple lattice model in figure F4.1
represents a solution of A and B. By statistical
thermodynamics, entropy S is

Polymer molcule
with x segmens
47

S = k lnW

where W is the number of possible

configurations of A and B solution.

48

10/24/2016

In the simple lattice, it is easy to count

the number of ways of putting NA A units
and NB B units into NA + NB lattice sites.
The result from combinatorial analysis is

For large NA and NB (i.e., for many

molecules) we can apply Stirlings
approximation for factorials
(ln n! n ln n n ) to get
ln W = NA [ln (NA + NB) - lnNA] + NB [ln (NA + NB) - lnNB]

49

50

We can even replace the ~ by a straight

equal sign because NA and NB will be so
large that Stirlings approximation is
effectively exact.
By definition of mole fraction

Introducing Avagadros number, L,

and realizing that R = Lk,
NA = LnA, and NB = LnB, we can
quickly derive
Smix = -R(nA lnXA + nB lnXB)

XA = NA/(NA + NB)
and
XB = NB/(NA + NB).
51

52

We find some interesting results when we

apply the lattice model to a polymer
solution.

F 2 shows a lattice model for one polymer

(component B) in solvent A.

The physics of mixing is unchanged, but

now we must consider the case where
one molecule is much larger than the
other molecule.

It is clear that the number of ways of

introducing the polymer molecule into
solvent A will be much less than the
number of ways of introducing the same
amount of monomer molecules B into the
same solvent.

53

54

10/24/2016

To count the polymer lattice

configurations we could go back to the
lattice model for a solution of A and B
and examine all of the W configurations.
For that large set of configurations we
must now reject all configurations that do
not have connected B molecules.

55

When compared to the monomer solution

problem (F 1), it is a much harder task to
count the number of configurations in
which all B units are connected into
chains of length x with excluded volume
on a lattice with solvent A.

57

The remaining configurations, which will

be much less than W, will be the number
of configurations of polymer B in solvent
A.
Therefore the entropy of polymer
solutions is much less that the
corresponding entropy for monomer
solutions of the same weight fractions A
and B.
56

An approximate calculation gives the

following result for the entropy of
mixing:

58

where

Likewise, nA will be the same for both

solution.
Consider two solutions of equal weight
fractions of component A and B monomer B
molecules in solvent A and a polymer of
connected B monomers in solvent A.
The mole fractions of A and B in the monomer
solution are identical to the volume fractions of
A59and B in the polymer solution.

The Smix expression differs only in the

value for nB. Because the polymer
solution connects many B monomers
into a single polymer, nB in the polymer
solution will be hundreds or thousands
of times lower than nB in the monomer
solution.
60

10

10/24/2016

Furthermore, in dilute solutions, the nB

lnXB and nB ln vB terms are the dominant
entropy terms.
Thus it can be concluded that the
entropy of mixing for polymer solutions
will be hundreds or thousands of times
lower than the entropy of mixing for
monomer solutions.
61

One thing that monomer solutions and

polymer solutions have in common is
that they both obey
conventional thermodynamics.
The deviations from ideality are direct
consequence of the size of polymer
molecules. The large size reduces the
entropy of mixing
which reduces the term TSmix.

62

When the entropy of mixing term is

small, it is much easier for the Hmix
term to assume a greater role.
containing hundred or thousand of segments

It also easy for Hmix to be greater

than TSmix and therefore for
polymers to be insoluble in many
solvents.
63

These segments- could freely make rotation at

fixed angle in its solution .
-- produced varity of conformations

(increasing in enthropy because the degre

e of freedom is increased )
64

Flory-Huggins Theory
We introduce a simple model F-2, for dealing
with polymer solutions called the Flory-Huggins
theory.

The theory predict Gm of polymer solution,

where it consider the polymer molecules to be
chains of segments (x), each segment being
equal in size to a solvent molecule.
65

This is a modified lattice theory which

take account of
1. the large differences in size between
solvent and polymer molecules
2. the solution is not ideal, means having
intermolecular interactions

66

11

10/24/2016

Molecular theory of polymer solution: Lattice Model (F.1)

1
Solvent molecule
Low molecular weight molecule

In brief, the theory attempts to estimate Hmix

using the lattice theory for solutions. We consider
nearest neighbor interaction between A and B
molecules. Then

F .1: A simple lattice model for a solution of A and B.

Solvent molecule

Polymer molcule
with x segmens

67

F 2: Polymer molecule B in a lattice model for a

solution in solvent A.

The interaction parameter describes the level of

interaction between pairs of A and B. A high positive
indicates a repulsive interaction and causes a
positive Hmix which tends to inhibit the solution
process.
A negative indicates an attractive interaction and
causes a negative Hmix which guarantees
dissolution.
The free energy of mixing in the
Flory-Huggins theory is

69

where NA is the number of molecules of

component A, nA is the number of moles of
component A, vB is the volume fraction of
polymer, and is the Flory interaction parameter.
68

Unfortunately, the Flory-Huggins theory is

not very good. In practice solution property
data cannot be predicted by using a single
value of the interaction parameter.
However, the interaction parameter, , which,
an essence, measures the solvent power of
the system and enable us to distinguish
between good solvent and poor solvent. (A
low value for Flory-Huggins parameter is
indicative of a good solvent)
70

Limitations of the Flory-Huggins theory

1. process of the segment-locating is purely
statistical.
2. neglect the contribution of excess entropy
from continual flexing of the chain in the
solution.
3. neglect any possible specific solventpolymer interaction
4. assume a uniform density of lattice site
occupation.
5. interaction parameter often concentration
dependent.
71

Heat of Dissolution and the Solubility Parameter.

Formula: Hildebrand and Scott,

Heat of mixing (Hm) of two liquids, for endothermic

mixing)

= Solubility parameter for both two 1,

and 2 liquids; 1 and 2 volume
fractions of liquid 1 and 2
72

12

10/24/2016

The solubility parameter, , is defined as

the square root of the cohesive energy
density (CED):

where EV is the molar energy of

vaporization and Vl is the molar volume
of the liquid 1.
73

For a substance of low molecular weight, the

value of the solubility parameter is often
estimated from the enthalpy of vaporization;
for a polymer, it is usually taken to be the value
of the solubility parameter of the solvent
producing the solution with maximum intrinsic
viscosity or maximum swelling of a network of
the polymer.

IUPAC:
Solubility parameter (of a polymer),
A parameter which is a characteristic of a
polymer used in predicting the solubility of
that polymer in a given solvent.
The solubility parameter is usually expressed
in (cal cm3)1/2 or, preferably, (J cm3)1/2 units.
The units must always be given;
1 (cal cm3)1/2 2.05 (J cm3)1/2.

74

The square of the difference between the

solubility parameters of two liquids decides the
magnitude of the heat of mixing.

Source: IUPAC Compendium of Chemical Terminology, 2nd

Edition (1997)
75

76

The above theory based on solubility parameter is

also valid fir polymer dissolution, which 1 denote for
polymer and 2 for solvent.

This square of the difference value should

be as low as possible, between10.5 16 to
expect for dissolution to occur.
When the solubility parameter 1 and 2
equal, H mixing becomes zero, mixing will
occur readily because of entropy factor

77

The equation only predicts that polymer will

dissolve only in solvents having solubility parameter
close to polymer

The theory not valid for crystalline

polymer, polar solvents or H positive.
Why ?
78

13

10/24/2016

Solubility parameter
= Solubility parameter of any
substance, may be obtained using
Small formula

= Solubility parameter of volatile

solvent can be calculated from the
latent heat of vaporization (H) using
formula,
[ H RT ]

DG
=

1/2

M/D
Where G is the molar attraction constant, D
density M is the molecular weight of the
segment.

Where R is gas constant, M is the molecular

weight, D density of the liquid
79

80

SOLUBILITY PARAMETERS OF
A FEW SOLVENTS AND POLYMERS
d (J-cm )
d (J-cm )
SOLVENT
POLYMER

Considering for poly(propylene)

- has segment; -CH (CH3)CH2-

- M = 42
- G value in Small formula,
-CH3=303; -CH2- =269; CH- =176 (J-cm3)1/2 mol
Hence, for PP
DG

(0.905)(303 +296+176)
=

42

= 16.1(J-cm3)1/2 mol

81

GROUP
CH3

G
(J-cm3)1/2/mole
303

GROUP
CH2

176

259

CH =

Poly(tetrafluoroethylene)

12.7

Carbon tetrachloride

17.6

Poly(dimethylsiloxane)

14.9

Toluene

18.3

Poly(ethylene)

16.2

2-butanone

18.5

Poly(propylene)

16.6

Benzene

18.7

Poly(butadiene)

17.6

Cyclohexanone

19.0

Poly(styrene)

17.6

Styrene

19.0

Poly(methylmetacrylate)

18.6

Chlorobenzene

19.4

Poly(vinyl chloride)

19.4

Acetone

19.9

Poly(vinyl acetate)

21.7

Tetrahydrofuran

20.3

Poly(ethylene terephthalate) 21.9

Methanol

29.7

Nylon 6,6

27.8

water

47.9

Poly(acrylonitrile)

31.5

(CO)2O

1159

Cl (primary)

419

OH

462

Cl (secondary)

425

269

OH (aromatic)

350

Cl (aromatic)

329

65

H (acidic dimer)

-103

84

NH2

463

Conjugation

17

NH

368

-cis

-14

125

-trans

-28

725

Six membered
ring

-48

NCO

733

Ortho

-19

439

Metha

-13

Cl2

701

para

-82

200
c

(aromatic)
CH = (aromatic)

O (epoxide)
c

O
(ether, acetal)

235

360

COO

668

538

CHO

599

239

3 1/2

Cont.

G
(J-cm3)1/2/mole

249

173
c

14.8

CH

CH2 =

3 1/2

n-hexane

82

VALUES OF MOLAR ATTRACTION

CONSTANT G

83

o
84

14

10/24/2016

THETA TEMPERATURE
From Flory,
[] M is directly proportional to the average
comformational size of a flexible polymer,

( 02)3/2

[] M

Where ( 02) is the near square end-to

end dimension of linear chains.

85

86

[] M = ( 02)3/2 3

[] =

According to Flory
(theta) state; special unperturbed state
temperature = the lowest temperatue at
which a polymer with infinite MW would be
completely miscible with a specific solvent.
is the critical miscibility temperature at
which the molecule assumes an
unperturbed conformation. Where no long
range or short range interaction.
At this temperature, the solution is said to
be pseudo-ideal and is free-rotation around
the bonds.

can be written

( 02)3/2 /M M1/2 3

The term ( 02)3/2 /M is a constant for a polymer

and independent of solvent and temperature
and can denoted by K

[] = K M1/2 3
[] =

KM1/2

at Flory temperature , = 1

Where is the intrinsic viscosity at the temp. in

a the solvent. K is around 1x 10-3 for a
number of polymer system

87

15