Necessity of polymer solution.

In carrying out polymerization reactions and study of kinetics.

In some polymer fabrication, such as casting of thin polymer films.
In the formulation of adhesives, surface coatings (paints and printing inks).
In the characterization of polymer structures (such as by NMR), and the determination of
molecular weight, and the molecular weight distribution.

In solution, polymer chains exist in various states.

1. Uniformly molecularly dispersed state(dilute solution)
2. Aggregating or micelle state; a number of polymer chains are assembled together.
3. Gel state; polymer chains form a network through the system.
4. Liquid crystal state; polymer chains align toward a certain direction.

Molecular dispersion Micelle/Gel state Liquid crystal state

Process of polymer dissolution : two step
1. Polymer swelling: the solvent diffuses into polymer masses to make a swollen polymer gel
2. Dissolution: swollen polymer gel breaks up to solution

Polymer Swollen gel Solvated state

Dissolution of polymers could be a very slow process, the higher the molecular wt the longer is
the required time; it can take days or even weeks for a particularly high mol wt polymer.
 G = change in free energy
Thermodynamic aspects H = change in enthalpy
T = temperature
The Gibbs Free Energy is defined as G = H - TS
S = change in entropy
In physical chemistry, we use G to predict the occurrence of a chemical or physical change
G < 0 spontaneous change (can occur by itself)
G = 0 process in equilibrium
G > 0 change cannot occur spontaneously
For dissolving polymer to occur spontaneously:
S is always positive because of increased conformational mobility of chain, and solution is
favored at higher temperatures. Thus, the sign of G depends on the magnitude of H

For - G: H must be SMALL

Note:
-H = solution state is lower in internal energy compared to pure polymer and pure
solvent state; polymer will be soluble.

+H = polymer and solvent do not want to mix,

However, if H < T S, polymer will be soluble (if small H).
From this consideration.
(1)Heating can increase the solubility as higher value of T would lead to higher TS
(2)It would be quite difficult to dissolve one polymer into another polymer, as S of mixing solid
polymer is relatively small.
(3)There is a limit to the increase in temperature (cannot go beyond the boiling point of
solvent), hence the process would be very dependent on the S of the mixing
Heat of Mixing for Binary (2-Component) System
2 components: (1) solvent and (2) polymer
2
1/2 1/2
E1 E2
Hmix = Vmix -
V1 V2 1 2

Vmix = total volume of mixture

V1 , V2 = molar volumes (MW / density) of 1 and 2
1 , 2 = Volume fraction of 1 and 2
E1 , E2 = Energy of vaporization of 1 and 2

E1 E2
V1 and V2 = Cohesive energy densities (CED) of solvent and polymer
 Before mixing After mixing

11 22
H mix 12
2
If we assume that there is no specific interactions (hydrogen bonding etc.) , then we can
assume that interaction 12 is some average from 11 and 22. Geometrical mean of small
numbers are more accurate. Thus,

H mix 11 22 11
22
2
1

11 2 11 22 22
2


2
11 22
2
1/2 1/2
E1 E2
Hmix = Vmix -
V1 V2 1 2

11 represents how molecules 1 (solvent) interact with itself i.e. Cohesive energy
density or energy of vaporization, E1 = energy of vaporization per volume
V1
 2
1/2 1/2
E1 E2
Hmix = Vmix -
V1 V2 1 2

Redefine with 1/2

solubility parameter, = E
V

The above equation can be rewritten as, which is known as Hildebrand equation
2
Hmix = Vmix 1 - 2 1 2

for H to be small (i.e. for a -G so that polymer dissolves): (1 - 2)2 must be small, or 1and 2
must be of same magnitude (if 1= 2, then dissolving only governed by entropy)

One must select a solvent with solubility parameter () similar to that of the polymer. In
general,
if there is no solvent-polymer interaction, one can safely predict solubility if|12|< 1. (For
non polar polymer)
where there is some weak solvent-polymer interaction (such as due to dipole moments and
weak polar groups), solubility might be possible with|12|< 4.
For those with very strong solvent-polymer interaction (hydrogen bonding), solubility could still
be possible with |12|15.
Determining 1 (Solubility Parameter of Solvent)

E1
= cohesive energy density (CED)
V1

Energy required to remove a molecule from its nearest neighbor. Similar to heat of
vaporization per volume for a volatile compound (e.g. solvent), which means the amount
of Energy required to transform a given quantity of a substance into a gas.
For a solvent, 1 can be calculated directly from the enthalpy of vaporization (Hvap):
R: gas constant (8.31 J/mol K)
E = Hvap - RT
T: temperature (K) (K = 273 + C)
V: molar volume: MW/density
Thus,
1/2
Hvap - RT
1 = V

units: MPa1/2 or (J/cm3)1/2 [note: 1 MPa1/2 = 1 J/cm3 = 0.49 (cal/cm3 )1/2 ]

E= total energy required to convert 1 mol of the compound into vapor state
V = molar volume(volume of 1 mol of the compound).

Example- determination of solubility parameter of water:

1 mol of H2O has a mass of 18 g and volume of 18 cm3 at room temperature,
So, the molar volume of water = 18 cm3mol-1.

The heat of vaporization of water is 40.66 kJ mol-1 ;E = 40660 J mol-1,

V = 18 cm3mol-1

= ( E/V )1/2
= (40660/18 J cm-3)1/2
= 47.5 J1/2cm-3/2
Determining 2 (Solubility Parameter of a Polymer)
There is no direct feasible measurement for since polymers degrade before they
vaporize. There are a few commonly used methods to estimate and hence 2 for
polymers:
a) Measurement of the polymer solubility in a range of solvents; or better, measurement of the
degree of swelling of a lightly cross-linked specimen of polymer in different solvents, otherwise
it will change the chemical composition of the sample, leading to an erroneous result. at
.the middle of the solubility range, or at maximum swelling, with the unmodified polymer is

taken as the value of the polymer.

The mid point is

taken as
b) is taken as the value of for the solvent which gives the maximum dilute solution
viscosity, i.e. by comparing for solutions of the same concentration of polymer in several
different solvents. The best solvent gives the highest viscosity since the polymer chain is most
expanded.

c) is calculated by the method of group contributions (G, molar attraction constants) by

Small's formula, 2= G/M .

This is an arbitrary method for estimating 2 value of a compound by considering the

contribution of each atom or group in the compound or the repeating unit in a polymer.
Through considering the structure, polarity, attractive and repulsive forces, each atom or group
of atoms is assigned a value known as the molar-attraction constant G. The solubility parameter
is then calculated from Smalls formula. As this method is based on different physical principle
from that of using heat of vaporization , the magnitude of 2 is here expected to be different,
where is the density and M the molar wt. of the repeating unit.

The G terms in the summation are values for each different chemical group comprising the
repeat unit of a polymer (or a solvent). There are several different tables of G values in the
literature. The various tables are internally consistent, but not there is not necessarily in
agreement between them, and Gs cannot be transferred from one to the other. Note that
hydrogen bonding groups such as amide, amine, hydroxyl and carboxyl present problems if such
interactions can occur between the solvent and polymer.
 0

Let us apply this scheme on H2O, which has a molecular wt of 18 g mol-1and density of 1 g cm-3

= G/M
= 1 g cm-3[(G(-OH) + G(-H)] / 18 g mol-1
= 1 g cm-3[(754 +140 ) J1/2cm3/2mol-1] / 18 g mol-1
= 49.6 J1/2cm-3/2

and this value is not far from that determined using heat of vaporization(47.5).
Ex: Poly(vinyl acetate) and poly(vinyl alcohol) have densities of 1.19 and 1.29 g cm-3
respectively. Calculate their solubility parameters, and comment about their relative
solubility in water.

Relatively, it is easier to dissolve PVA in water than to dissolve PVAc in water.

 Solubility of random copolymer: 2 = iwi
where i = solubility parameter of homopolymer that corresponds to monomer i in the
copolymer and wi =weight fraction of the repeating unit i in the copolymer.
Alternating copolymers can be treated by taking the copolymer repeat unit as that of a
homopolymer.
No satisfactory method exists for assigning values to block or graft copolymers.

General Rules for Solubility

Polymer and solvent combinations with different levels of H-bonding reduces solubility
Rate of solubility (in a given solvent at a particular temperature):
Increases with short branches
Decreases with long branches (entanglements)
Decreases with increasing MW
Higher temperatures increase solubility: Example: PE (2 = 16.2 ) will not dissolve in any
solvent at room temperature but dissolves in many non-polar solvents at 100 C.
Crystallinity reduces solubility
Crosslinking eliminates solubility
Some examples where solubility is less
If strong POLAR or H-BONDING in SOLVENT and polymers are listed as poorly,
moderately, or weakly H-bonded solubility will be less.
Even if 1 2, solubility may not be achieved if polymer and solvent have different
tendencies for H-bond formation.
# For Polystyrene.
PS poorly H-bonded
2 = 18.4 MPa1/2
Highly soluble in poorly H-bonded solvents with similar 1
Thus, highly soluble in benzene (1 = 18.8 MPa1/2) and toluene (1 = 18.8 MPa1/2)
#For PMMA
PMMA moderately H-bonded
2 = 20.7 MPa1/2
Highly soluble in moderately H-bonded solvents with similar 1
Thus, highly soluble in acetone (1 = 20.3 MPa1/2).
Behavior of Polymer in Solvent
Once a solvent has been selected to dissolve a polymer, one must consider how the polymer
chains behave in that solvent.

Conformation: Conformation: expanded

balled/coiled up
1 - 2 4 good solvent
1 - 2 > 4 MPa1/2 poor
solvent higher temp.

Lower temp. Polymer-solvent

interactions dominate
Polymer-polymer
interactions dominate

Switch from conformation-to-conformation due to backbone bond rotation.

The above polymer chains have occupy different volumes (i.e. have different hydrodynamic
volumes).
Hydrodynamic Volume:
average statistical volume (size) of polymer in solution
Average shape of chain assumed to be a sphere
Depends on: solvent interactions (also, branching, flexibility, MW, intermolecular interactions).

s = radius of gyration Rg
r = end-to-end distance RMS distance of the chain segment
For an isolated chain, not possible to assign a unique (elements of the chain) from its
value of r since the chain conformation (and hence r) center of gravity (i.e. center of mass
is constantly changing of the molecule): s21/2
But, each conformation has a unique value of r. Thus,
some values of r are more probable than others. So,
the probability distribution of r is represented by:
Root mean square (RMS) end-to-end distance r21/2
 s 2 = so22

2
s 2 = mean square radius of
r 2 = ro22 r = mean square end-to end
gyration
distance
so = mean square radius of
ro = mean square end-to-end distance
gyration of unperturbed chain
of unperturbed chain
= expansion factor
= expansion factor

Unperturbed dimension: size of polymer chain exclusive of solvent effects

Expansion Factor (): - due to free rotation, intramolecular, steric and polar interactions
- arises from solvent and polymer interactions
For linear chains (not extended beyond most probable shape), the relation between end-to-end
distance and Rg is , r 2 = 6 s 2
Expansion Solvent Conformation Note
1/2 factor
r2 perturbed or actual size in
= solvent >1 Good Expanded r2 > ro2
1/2
ro2 unperturbed size: no solvent
effects <1 Bad Collapsed r2 < ro2

collapsed random coil

expanded =1 Theta Statistically r2 = ro2
() random coil
(unperturbed)
bad
theta
good
The Flory-Huggins Theory (to calculate the entropy of mixing)
In 1942, Flory and Huggin applied a lattice model to obtain an approximation
for entropy change for the mixing of polymer in a solvent.
Entropy of mixing of monomer in a solvent
Assumptions:
No interaction between the particles
Not two particles on one lattice
position (one particle per lattice
position) take excluded volume into
account
All lattice positions are occupied (n =
n1 + n2)
The above figure is a representation of 2D lattice containing solvent molecule
() and solute ().
According to Boltzmann relation, S = k ln .[1]
Where, = number of different ways of arranging n1solvent molecules and
n2solute molecules available to the system.
n = n1+ n2 = total number of lattice point.
k = Boltzmanns constant = 1.3806x10-23JK-1
 As,
The entropic contribution to G is thus seen to always favor mixing if the
random mixing approximation is used.

Entropy of mixing of polymer in solvent

Assumptions
No interaction between the particles
Not two particles on one lattice position (one particle per lattice position) take
excluded volume into account
All lattice positions are occupied (n = n1 + Nn2)
Polymerize the particles of type 2 number of possible configurations is
drastically reduced (calculate with lattice model):
The entropy S is given by the number of possible configurations of
the particles on the lattice:
S kB = ln
with Ansatz of the possible configurations of the polymer (by Flory):

+1

Lattice occupied with i polymer chain segments, place segment number i+1:
The probability function is given as
= N!/(n1! n2! )........................... [2]
Thus, equation [1] becomes,

S = k ln = k ln{N!/(n1! n2! ) } = k lnN! k ln n1! k ln n2!

Using Stirlings approximation, lnn! = n lnn n, This leads to the expression

S = -k (n1 ln X1+ n2 ln X2)...................[3]

Where, mole fraction of solvent, X1= n1/N and mole fraction of solute, X2= n2/N,
N = n1+ n2, and n1= X1N and n2=X2N, hence [3] can also be written as

S = -k N(X1 ln X1 + X2 ln X2)

For mixing 1 mole (1molar)of materials(solvent and solute),

N = N0= Avogadros number, kN0= R,

therefore the molar entropy of mixing in case of ideal solution would be

Sm= -R(X1 lnX1 + X2 lnX2).......... [4]
Applying the lattice model to a polymer solution, we would expect the entropy to be much
smaller because of the linkage of individual repeating units along the polymer chain.

Assuming each polymer chain is divided into r segments and each segment is equal to the size of
a solvent molecule.
If there are number of solvent molecules n1 and n2 polymer chains, the total number of the
lattice sites is then N= n1+ r n2

Then the lattice volume fractions of solvent 1and polymer 2 are given by

1= n1/N = n1/(n1+r n2)

and
2= n2 /N=n2/(n1+r n2)

Thus, The entropy of mixing polymer in a solution is, S = -k (n1 ln1+ n2 ln 2)[5]
The value of S for mixing of polymer and solvent is generally quite small, thus for TS > H,
H must be as small as possible.
The assumptions/limitations of Flory-Huggins theory are

Applicability only to solutions that are sufficiently concentrated that they have uniform
segment density

There is no volume change of mixing (whereas favourable interactions between polymer and
solvent molecules should result in a negative volume change)

There are no energetically preferred arrangements of polymer segments and solvent molecules
in the solution

Quasi-solid (semi solid) lattice in the liquid

Inter-changeability of segments (not necessarily the same as the polymer structure units) of
polymer and solvent molecules in the lattice

Polymer molecules are of same size

Average concentration of polymer segments in cells adjacent to cells unoccupied by the

polymeric solute is taken to be equal to the overall average concentration
The Phase diagram of polymer solution:
The phase separation temperature (and hence, the cloud point) is dependent on polymer
concentration. Therefore, temperature-composition diagrams are used to display
thermoresponsive behavior over a wide range of concentrations. Phases separate into a
polymer-poor and a polymer-rich phase. However, since polymers display a molar mass
distribution this straightforward approach may be insufficient.

Polymers dissolve in a solvent when the Gibbs energy of the system decreases, i.e., the change
of Gibbs energy (G) is negative. G is determined by the enthalpy of mixing (H) and entropy
of mixing (S). Without interactions between the compounds there would be no enthalpy of
mixing and the entropy of mixing. The ideal entropy of mixing of multiple pure compounds is
always positive (the term -TS is negative) and G would be negative for all compositions,
causing complete miscibility. Therefore, the fact that miscibility gaps are observed can only be
explained by interaction. In the case of polymer solutions, polymer-polymer, solvent-solvent and
polymer-solvent interactions have to be taken into account. A model for the phenomenological
description of polymer phase diagrams was developed by FloryHuggins solution theory.

The minimum free energy can
be lowered by going to
compositions A1,B1 to give free
energy F1 etc. And as A and B
continue to dissolve more and
more of each other, free energy
continues to drop. Minimum
energy for homogeneous single
phase, energy Fn i.e no phase
separation occurs in this case.
Composition overall determines
the state of the mixture.
Minimum in energy occurs at F3 when the
representative points on the free energy curve are
joined by the lowest straight line: common tangent
construction.
This case have phase separation into compositions
cA and cB, with phases and .
For compositions
c < cA have phase
cA < c < cB have +
cB<c have just .
cA and cB define solubility limits.
 Binodal curve

The locus d2f/dc2 = 0 is called the spinodal curve.

Necessary condition for homogeneous mixing to occur is for d2f/dc2 0 is

called the binodal curve.
 T

c

If the enthalpic interactions are disfavourable, the mixture will exhibit an upper critical solution
temperature-critical point is on the top of the phase separa-tion region. Immiscible at lower T
due to disfavourable enthalpic Interactions and miscible at higher T due to favourable enthalpic
interactions. In the T, c the phase diagram has the form shown in the figure, i.e. the poor solvent
region corresponds to T
Examples: poly(styrene) in cyclohexane, poly(isobutylene) in benzene, acetylcellulose in
chlorophorm.
The UCST (if it exists) increases and shifts into the
solvent-rich region when the molar mass of the
polymer increases. Ex- Polystyrene and polybutylene
blends as a function of Polystyrene
molecular weight M(PB) = 2350
a. M(PS) = 2250
b.M(PS) = 3500
c.M(PS) = 5200
In case of lower critical solution temperature)-critical point is on the bottom of the
phase separation region, solution is miscible at lower T due to favourable enthalpic
interactions. Immiscible at higher T. Then the T, c phase diagram has the form shown
in the figure below, i.e. the poor solvent region corresponds to T>

Examples: poly(oxyethylene) in water, methylcellulose in water, in general - most of

the water-based solutions.
The reason: increase of the so-called hydrophobic interactions with the temperature
(organic polymers contaminate network of hydrogen in water and water molecules
become less mobile (solvated), i.e. they lose entropy - this unfavorable entropic factor
for polymer- water contacts is more important at high temperatures).
 Different polymers have different segments on their backbones. The ease of movement of
these segments (portions of the chain) depends on the structure, physical environment of the
chain etc. of the segment. Any movement of these segments require energy which is kinetic in
this case. Then each different polymer would have different energy requirement for the
movement of these segments. Below glass transition temperature, these segments do not have
sufficient energy to move. So, if you apply some stress, say if you try to bend a polymer which is
below its Tg then the segments wont be able to move into new positions to relieve the stress
which you have placed on them; which will make the polymer brittle. Above Tg they would, so
they would be flexible. Tg is a property related with the amorphous regions of the polymer, not
crystalline.
 Factors affecting Tg
1. Chain Length.
As molecular weight increases, Tg also increases
As molecular weight decreases, Tg also decreases
More end groups
Easier movement of molecules
More inherent free volume in the polymer
2. Plasticizers. Their small molecules fit in between the chains. Causes chains to be less tight
amongst themselves
3. Chain stiffness and side groups.
Chains that have difficulty uncoiling have higher Tg
Chain stiffness is related to higher energy level
Bulky side groups hinder rotation
4. Copolymers. Tg will be some kind of average between the two monomeric materials.
5. Pressure
6. Factors governing conformation
Potential energy hindering internal rotation
Packing considerations
Repulsive forces and Van Der Waals Forces, Hydrogen bonding, Electrostatic interactions
What if both melting and glass transition appear in the differential scanning calorimeter (DSC) spectrum
of a polymer sample?

It is absolutely OK. Remember, most polymers are semi-crystalline, i.e. have both amorphous and
crystalline regions

amorphous
polymer
semi-crystalline
polymer
Polymer degradation is a change in the propertiestensile strength, color, shape, etc. of a
polymer or polymer-based product under the influence of one or more environmental factors
such as heat, light or chemicals such as acids, alkalis and some salts. These changes are usually
undesirable, such as cracking and chemical disintegration of products or, more rarely, desirable,
as in biodegradation, or deliberately lowering the molecular weight of a polymer for recycling.
The changes in properties are often termed "aging.
 Biodegradable Polymers

O
Carbonyl bond to N
S

A.

O H2O O

R1 C X R2 R1 C OH
+ HX R2

Where X= O, N, S

O O
O

R1 C O R2 R1 C NH R2
R1 C S R2

Ester Amide Thioester

Chemical degradation-
1. Solvolysis
Step-growth polymers like polyesters, polyamides and polycarbonates can be degraded by
solvolysis and mainly hydrolysis to give lower molecular weight molecules. The hydrolysis takes
place in the presence of water containing an acid or a base as catalyst. Polyamide is sensitive to
degradation by acids and polyamide mouldings will crack when attacked by strong acids.

2. Polymer Oxidation

Examples of chemical domains that

are susceptible to oxidative
degradation. * denotes sites of
homolysis or heterolysis
3.Biological degradation.
Biodegradable plastics can be biologically degraded by microorganisms to give lower molecular
weight molecules. To degrade properly biodegradable polymers need to be treated like compost
and not just left in a landfill site where degradation is very difficult due to the lack of oxygen and
moisture.
Factors that accelerate polymer degradation
More hydrophilic backbone.
More hydrophilic end groups.
More reactive hydrolytic groups in the backbone.
Less crystallinity.
More porosity.
Smaller device size.

Methods of studying polymer degradation

Morphological changes (swelling, deformation, bubbling, disappearance)
Weight lose
Thermal behavior changes
Molecular weight changes
Change in chemistry