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Polymer molecular weight (Mw)

Mw controls many physical properties of polymers



A-Transition Temperature: From one phase to other
( From liquids to waxes to rubbers to solids )
B-Mechanical Properties:
(stiffness, strength, viscoelasticity, toughness,
and viscosity)
Thus Mw is low, the transition temperature and
mechanical strength low
Strength and molecular weight have approximate
inverse relation.

A is a constant and M is the molecular weight
S
0
is strength at infinite molecular weight.




polymers property is rather a function of molecular
distribution weight,P(M).



)] ( [ / M p F A S S = o
M A S S / = o
Or a function of average molecular weight.

> < = M A S S / o
Effect of MW on Property of the Polymers
Tensile Strength as a function of MW
The tensile strength is the stress needed to
break a sample (Pascals or psi). The tensile
strength is an important property for polymers.
% Elongation to Break

The elongation-to-break is the strain on a sample
when it breaks. This usually is expressed as a percent.
Young's Modulus
Young's modulus is the ratio of stress to
strain. It also is called the modulus of
elasticity or the tensile modulus.
Rigid materials, such as metals, have a high
Young's modulus but low Mw polymers will
have low modulus.
Degree of Polymerization and Molecular weights
X
n
= ---------
1
1-P
M
n
= M
0
---------
1
1-P
X
w
= ---------
1-P
M
w
= M
0
---------
1-P
1+P
1+P
M
w
1+P
M
n
PDI
Depending on statistical methods, the following
molecular weights of polymer are determined
Weight average molar mass or Mw
Number average molar mass or Mn
Viscosity average molar mass or M
Z average molar mass or Mz
Typical molecular weights
distribution curve
Mn < Mv < Mw < Mz
Polydisperse sample:
having broad range of
size,shape and mass
characteristics
Monodisperse
sample: uniform
size, shape and
mass
distribution
Common
Not Common
Polydispersity of a sample is defined as ratio
of Mw/Mn


A-In step growth polymerization it is about 2
B- In addition polymerization it varies from
10- 20
C- In living polymerization its value is nearly 1
Polydispersity in polymer varies with
mechanism of polymerization
The resistance to flow of polymer solution
through a capillary is very informative as

A- It provides information on the size of polymer
chains.

B-Its flexibility and shape in solution.

C-Its interactions with solvent in which it is
dissolved.
Viscosity of dilute polymer solution is higher
than ordinary solutes.
Ubbelohde viscometer by German chemist
(1877-1964).
Ubbelohde type viscometer or suspended-
level viscometer is capillary based viscometer
used to measure viscosity of polymers
Where, t0 and 0 are the elution time and
density of the pure liquid. When the solution is
very dilute
The so-called specific viscosity
becomes:
This specific viscosity is related to the concentration of the analyte.
Concentration dependence of reduce viscosity.
This specific viscosity is related to the concentration of the
analyte.
Where, sp/c is
called the
viscosity number
Or reduce
viscosity
Concentration dependence of inherent
viscosity
lnq
r
C
q q
k
2
C
+
........
k' - k'' should equal 0.5
Inherent and reduce viscosity are having
common intersect
Typical Huggins and Kraemer Plots (note common
intercept for both curves)
Intrinsic viscosity [] is a measure of a solute's
contribution to the viscosity of a solution and
related to the molecular weight of the polymers as
a and K, depend on the particular polymer-
solvent system.
Also, the molecular weights of two different
polymers in a particular solvent can be related
using the Mark-Houwink equation when the
polymer-solvent systems have the same intrinsic
viscosity:
a ~ 0.5 (randomly coiled polymers)
~ 0.8 (rod-like, extended chain polymers)
K between 10
-3
and 0.5
K M
a
Mark-Houwink equation |q|
3
2
1
2
3 2
0
2
3
2
2
0
) (
) (
] [ o |
o |
q M
M
r
M
r
= =
[q] intrinsic viscosity related to size (r
0
)
| is Flory constant (~310
24
mol
-1
)
|
|
.
|

\
|
M
r
2
0
is a constant
At u temperature, o = 1
2
1
] [ M K = q
At other conditions
a
M K = ] [q
In the above equation the intrinsic viscosity is written along
with expansion factor and the unperturbed end-to-end
distance
Intrinsic viscosity and unperturbed dimension of
polymer chains
In a theta solvent, the expansion factor (o) is 1
Thus [q] proportional to the square root of molecule
weight ( M

) and the 3/2 power of
[q] = | = | ( )
3/2
M
1/2
= | ( )
3/2
M
1/2
o
3
< r
2
>
< r
2
>
3/2
< r
0
2
>
M
M M
< r
2
> = o
2
<

r
0
2
>
< r
0
2
>/ M
[q] = |
3/2
M
1/2
< r
0
2
>
M
Effect of Mw on Intrinsic Viscosity of Polymer
The Ubbelohde capillary viscometer
The most useful kind of viscometer for determining
intrinsic viscosity is the "suspended level" or Ubbelohde
viscometer.







B
A: Plug while drawing fluid
into capillary
D: Timing lines
C: Pressure
equilibration arm
Little bulb, whose
volume = V.
Q = V/t
flow

Capillary
Big Bulb/Reservoir



Single point estimation of intrinsic viscosity by
Solomon and Ciuta is sufficiently accurate
The intrinsic viscosity is determined by extrapolation
of the ratio
sp
/C through various concentrations to
zero concentration . This is impractical for
chromatographic detection and it also turns out to be
unnecessary wastage of time.
[q] =
C
[2 ( q
sp
-ln(q
sp
+ 1)) ]
1/2
Dimension of polymer chains and intrinsic
viscosity
1- Root-mean-squared end-to-end distance of
Polymer Chains < r
2
>
1/2

2-Hydroynamic Radius of Polymer Chains (R
h
)

3-Root mean squared radius of gyration < r
g
2
>
1/2

4-

The simplest conformation of polymer chain is fully extended
chain.The end to end distance in this idealized model for chain
length is
r = n l
Root mean square end-to-end distance
and root mean square radius of gyration
The average root mean square end-to-end distance for the
chain, <r
2
>
1/2
, turns out to be l times the square root of N. In
other words, the average distance scales with N
0.5
.



Average end-end distance of polymer (<r
2
>
1/2
)
A quantity frequently used in polymer physics is
the radius of gyration <r
g
2
>
1/2
. it is root-mean-
square (r.m.s.) distance of all the bonds from the
centre-of-mass of the chain, averaged over all
possible conformations.
< r
2
>
1/2
= N l
< r
g
2
>
1/2
= ------
N
l
6
Root-mean-squared end-to-end distance of
Polymer Chains and Intrinsic
Viscosity
Flory-Fox expression for the root-mean-squared end-
to-end distance of polymer molecules in solution.
The constant u for polymer molecules in a good
solvent has been found experimentally to be of
2.1 10
21
dl / mol cm
3
.
< r
2
>
1/2
< r
2
>
1/2
= [q] M/|
Hydroynamic Radius of Polymer Chains ( R
h
)
and Intrinsic viscosity.
Based on Einstein viscosity relation
The hydrodynamic radius R
h
may be calculated using
Einstein viscosity relation, considering hydrated polymer
molecules as hydrodynamic spheres that would increase
the viscosity to the same extent as solid spherical
particles of volume V
e
:
where M = polymer molecular weight (g/mol), N =
Avogadro's number, and V
e
= the volume of an
equivalent spherical particle (cm
3
). Since
Thus, for each
polymer is
simply 3.1- fold
greater than R
h
.
< r
0
2
>
[q] =
M
2.5 NV
e
R
h
= ------------ (cm)
3[q]M
10 H N
1/3
Ve = 4/3 t R
h
3
The and M are proportional to the number of
bonds or n.
Therefore, is a constant for a particular
polymer that is independent of molecular weight.
Thus above equation is simplified to
Where , K is a constant
For polymers in non-theta solvents, o will no longer be
one hence [q] will not be square-root dependence on
molecular weight.
where o may have molecular weight dependence of
its own. Thus for non theta condition it is written as

[q|

= K M
1/2
o
3
[q|

= K M
1/2
[q|

= K M
a
< r
0
2
>/ M
< r
0
2
>
Effect of branching on pervaded volume between a linear
chain and a branched chain with the same total chain
length
The hydrodynamic volume is smaller with the same mass
of polymer molecule with high density, producing a lower
Intrinsic Viscosity.
The Mark-Houwink plot is the central plot of polymer
structure analysis. It reflects structural changes in the
polymer, such as polymer branching and chain rigidity.
Mark-Houwink constant (a) related to the structure of
polymer. If its value varies from 0 to 0.1 = spherical, 0.35 to
0.80 = random coil, and 1.5 to 2 = rigid rod structure.
More Precise information about the values of
a in Mark-Houwink Equation
1- Value of a = 0 Sphere shape polymer molecules
2- = 0.5 - 0.8 Random coil structure
(0.5 Flory u temperature and
0.8 for thermodynamically good solvent
3- = 1.0 Stiff coil structure
4- = 2.0 Rod shape structure
[q|

= K M
a
Branching index
The branching index measures the effect of long-
chain branches on the size of a macromolecule in
solution.
It is defined as:
g = <s
b
2
>/<s
l
2
>
where s
b
is the mean square radius of gyration of
the branched macromolecule in a given solvent,
and s
l
is the mean square radius of gyration of an
otherwise identical linear macromolecule in the
same solvent at the same temperature.
A value greater than 1 indicates an increased
radius of gyration due to branching.

Intrinsic viscosity and degree of long chain branching
in polymers

Intrinsic viscosity is related to the degree of long chain branching
in polymers through the following factor (g), which is analogous to
ratio of mean square radius of gyration g.
Where, []
M,br
denotes the intrinsic viscosity of the branched
polymer at molecular weight M
and []
M,lin
is the intrinsic viscosity of the corresponding
linear polymer at the same molecular weight M.
is a structure value having an average value of
approximately 0.8
g' =
[q|
M,
[q|
M,
br
lin
Intrinsic viscosity versus molecular weight plots (Mark-
Houwink plots) for linear and branched PVA polymers.
Branching distribution overlaid with the weight fraction
distribution of the branched PVA sample.
Left hand axis shows the number of branches
Zimm and Stockmayer equations for degree of
branching
R a n d o m , T r i - f u n c t i o n a l m o n o d i s p e r s e
g
M
=
1 +
M
B
7
1 / 2
+
B
M
4
9 H
1 / 2 -
S t a r b r a n c h m o n o d i s p e r s e
g
M
=
M
B 6
B
M
+ 1
(
) B
M
+ 2 ( )
I n e a c h o f t h e s e e q u a t i o n , t h e n u m b e r o f
b r a c h e s ( B M ) i s r e l a t e d t o a n e n t i t y ,
w h i c h i n t u r n r e l a t e d t o

a s ,
g
M
'
=
g
M
b
w h e r e b i s s t r u c t u r e f a c t o r f o r t h e p o l y m e r
g
M
' =
[ q |
M ,
b r
[ q |
M , l i n
g
M
b
g
M
To determine the branching number( B
M
) for a branched
polymer, we need to know its structure factor b , to
decide which branching calculation has to be made. The
average value of b is 0.8. This can be determined either
from the Mark-Houwink constants a of the polymer, or
by inspection from a linear reference sample.
Inject a series of Narrow Standards of known Molecular Weight.
Measure the Retention Volume (RV) of the resulting peak apex.
Construct a calibration curve of Log(MW) vs. Retention Volume.
GPC Theory : In Gel Permeation Chromatography
Intermolecular forces:
1-The intermolecular forces for polymers are the
same as for small molecules.
2-Though, the magnitude of their intermolecular
forces can vastly exceed those between small
molecules.
3-The presence of strong intermolecular forces is
one of the main factors leading to the unique
physical properties of polymers.
4-These intermolecular forces are following types.
A-Dispersion Forces:

B-Dipole-Dipole Forces:

C-Hydrogen Bonds:
A-Dispersion Forces

1-Dispersion forces are due to instantaneous dipoles
that form as the charge clouds in the molecules
fluctuate.

2-Dispersion forces, the weakest of the intermolecular
forces.

3-These only forces possible for non-polar polymers
such as polyethylene.

4-Dispersion forces depend on the polarizability of a
molecule.

5- Large polymers with high molecular weights can
have significant dispersion forces.

Ultra high molecular weight polyethylene
(UHMWPE), which has a molecular weight in excess
of 3,000,000 g/mole, is used to make
bulletproof vests.
B-Dipole-Dipole Forces

Dipole-dipole forces result from the attraction between
polar groups,such as those in
1- polyesters and,
polyester called poly(ethylene terephthalate) (PET)
2- Vinyl polymers with chlorine pendant groups.
Polyvinyl chloride.

C-Hydrogen Bonding
Hydrogen bonding can take place when the
polymer molecule contains -OH or -NH groups.
Hydrogen bonding is the strongest of the
intermolecular forces.
Polymers such as
1-Poly(vinyl alcohol) and,
polyamide(nylon)
2-Polyamides, polpeptides have hydrogen
bonding
D-Electrostatic interactions

In addition to hydrogen bonding, there
are electrostatic interactions, such as
those between COO and NH3+ groups
of the side chains.
1-Interactions between polymers influence the
physical properties,
both in equilibrium and
nonequilibrium conditions.
Manifestation of Molecular Interactions in
Polymers
2-Most thermoplastics are polymers with
high molecular weight that are associated
through the van der waals forces, dipole-
dipole interactions etc
Physical properties
1- Solution properties.
(Interactions with the solvents:
solubility, viscosity etc)
2- Phase Transition Temperatures.
Glass Transition Temperature(Tg)
3- Mechanical Properties.
(Tensile strength, elongation, retraction
forces, thermo mechanical behavior)
4- Stability toward heat and chemicals.
(Decomposition on heating, and
corrosive effect of solvent)
5- Miscibility with other polymers
(Extent of Blending or mixing)
Retraction forces in elastomers
They return to original shape due
to intermolecular forces
State of material is also influenced by these
Intermolecular forces

Textbooks:

1. Billmeyer Jr.(FW).Text book of Polymer Science. 3rd Ed. 1994, Wiley
Interscience, New York.

2. Fried (JR). Polymer Science and Technology. 2002, Prentice-Hall ofIndia

3. Stevens(MP), Polymer Chemistry: An Introduction. 3rd Ed. 1999, Oxford
University Press, New York.

4. Seymour (RB). Carraher Jr (CE). Polymer Chemistry.1991, Marcel-Dekker,New
York.


S.N.

Particulars

Contact





Hrs

1.

Introduction: General idea of the polymers and their

4



classifications, molecular forces and chemical bonding; Polymers in





technological and biomedical fields.



2.

Polymer chains and molecular weights: Degree of





polymerization, Number and weight average molecular weights.

6



Molecular weight dispersity and characteristics of polymers, Weight





and composition heterogeneity in polymers. Polymer chain





dimension and solution viscosity. Thermal and spectral





characteristics of polymers.



3.

Methods of polymer synthesis: Synthesis of polymers using bulk,

6



solution, emulsion, suspension and interfacial route of





polymerization and characteristics of polymers. Addition and step





growth polymers.



4.

Technological polymers: Polymer blends, Polymers Composites,

6



Polymer films, Resins, Foams, Polymer Liquid Crystals and





Engmeering Plastics, Smart and Responsive Polymers. Polymers for





Device Applications, Biodegradable Polymers. Conducting polymers



5.

Industrial Polymers: Vinylic and Phenolics, Polyesters,

6



Polyamides, Polyphosphazenes, Polysilanes, Polysiloxanes,





Coordination and Organometallic polymers, Polyacrylates