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Polymerisation : Molecular Weight

and Structure
n
There are two major classes of polymer
formation mechanisms
Addition polymerization: The polymer grows by
sequential addition of monomers to a reactive site
Chain growth is linear
Maximum molecular weight is obtained early in the
reaction
Condensation Polymerization/Step-Growth
polymerization: Monomers react together to make
small oligomers. Small oligomers make bigger ones,
and big oligomers react to give polymers.
Chain growth is exponential
Maximum molecular weight is obtained late in the
reaction
Polymerization Methods
H H
A. Free Radical Polymerization
1. Initiation
Free radical initiator
(unpaired electron)
C C
H
H H
H
monomer
C C

H
H
H
R
H
R

Radical
transferred
C C
H
H
o bonds
t bond
R
H
H
C
H
H
C
R
sp
2
carbons
sp
3
carbon
Addition polymerization
Polymerization Methods
A. Free Radical Polymerization
2. Propagation
C C
H
H H
H
C C

H
H
H
R
H
C C

H
H
H
C
H
H
H
C
H
H
R
C C
H
H H
H
C C

H
H
H
C
H
H
H
C
H
H
C
H
H
C
H
H
R
H
H
C
H
H
C
R
H H
C C
H
H
Both carbon atoms will
change from sp
2
to sp
3
.
Polymerization Methods
A. Free Radical Polymerization
3. Termination
C C

H
H
H
R
H
C C

H
H
H
R
H
R

+
C C
H
H
H
R
H
R
C C

H
H
H
R
H
+
C
H
H
C
H
H
C
H
H
C
H
H
R R
Intentional or unintentional molecules/impurities can also terminate.
Addition Polymerization
Propagation
nA
In A A A A
n
A*
A A A A A
m
In A A A A
n
A
*A A A A A
m
Combination
*A A A A A
m
In A A A A
n
A
B A A A A
m
Disproportionation
Termination
Reactive site is consumed
A
In A A A A
n
A
A*
Chain Transfer
New reactive site
is produced

MW
k
propagation
k
ter mination
MW
% conversion
0 100
In*
A
Initiation
In A A A A*
Step-Growth Polymerization
Stage 1
Consumption
of monomer
n n
Stage 2
Combination
of small fragments
Stage 3
Reaction of
oligomers to give
high molecular
weight polymer
Step-Growth Polymerization
Because high polymer does not form until
the end of the reaction, high molecular
weight polymer is not obtained unless high
conversion of monomer is achieved.

X
n
=
1
1 p
X
n
= Degree of polymerization
p = mole fraction monomer
conversion
1
10
100
1000
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction Conversion (p)
D
e
g
r
e
e

o
f

P
o
l
y
m
e
r
i
z
a
t
i
o
n
Nylon-6,6
Cl Cl
O O
4
H
2
N NH
2
4
Adipoyl chloride 1,6-Diaminohexane
Cl N
H
N
H
H
O O
4
4
NaOH
HO N
H
N
H
H
O O
4
4
n
6 carbon
diacid
6 carbon
diamine
Nylon-6,6
Diamine, NaOH, in H
2
O
Adipoyl chloride
in hexane
Nylon 6,6
Nylon-6,6
Diamine, NaOH, in H
2
O
Adipoyl chloride
in hexane
Nylon 6,6
Since the reactants are in different
phases, they can only react at the phase
boundary. Once a layer of polymer forms,
no more reaction occurs. Removing the
polymer allows more reaction to occur.
MOLECULAR WEIGHT AND
MOLECULAR WEIGHT DISTRIBUTION
What is n?
n is degree of polymerisation
Molecular Weight
When we talk about molecular weight in terms of polymers, we are really
talking about the length of the individual chains.

The polymerization process is subject to variation so there is no single
chain length, there is actually a wide range of lengths, so when we
discuss molecular weight, we really mean the average molecular
weight of the material. This average is found by measuring samples of
the material as it is produced.
Molecular Weight
There are two different categories of molecular weight average
that are commonly used:

The first is the Number Average Molecular Weight ( )


The second is the Weight Average Molecular Weight (

)

Another important aspect of the molecular weight distribution
is the shape of the curve.
Molecular Weights
Not only are there different structures (molecular arrangements)
but there can also be a distribution of molecular weights
(i.e. number of monomers per polymer molecule).
20 mers
16 mers
10 mers
Average molecular weight =
monomer monomer
M M 3 . 15
3
10 16 20
=
+ +
This is what is called number average molecular weight. (Mn)
Molecular Weight
The figure to the right represents a
typical molecular weight
distribution.

The vertical axis represents
the number of chains at that
length.
The horizontal axis represents the
different chain lengths.

Notice that the longer chains are to the left on the graph and the shorter chains are to the right.
Molecular Weight
The Number Average
Molecular
Weight ( ) is the total
weight of the polymer
molecules divided by the
total number
of polymer molecules.
Molecular Weight
Number Average Molecular Weight (

) Example:
We have:
10 moles of Polyethylene (PE) that are 500 monomers long
5 moles of PE that are 100 monomers long
5 moles of PE that are 800 monomers long

What is ?
Molecular Weight
Number Average Molecular Weight ( ) Example:
Each monomer is 2 Carbons and 4 Hydrogens
10 moles X 500 monomers = 5,000
5 moles X 100 monomers = 500
5 moles X 800 monomers = 4,000
Total number of moles = 20 = (10 + 5 + 5)
Total number of monomers = 9,500

What is ? 9500/20

= 475 monomers
The average chain is 475 monomers long
Molecular Weight
Look at the numbers from the previous example:
10 moles of PE that are 500 monomers long
5 moles of PE that are 100 monomers long
5 moles of PE that are 800 monomers long

Calculate the
Molecular Weight

Calculate the
Find the weight fractions:
10 x 500 / 9500 = 52.6%
5 x 100/ 9500 = 5.3%
5 x 800 / 9500 = 42.1%


= (0.562 x 500) + (0.053 x 100) + (0.421 x 800) = 605.3
monomers long
Molecular Weight
The Weight Average Molecular
Weight ( ) takes into account
that the larger molecules contain a
much higher amount of the
molecular mass of the polymer.
The Weight Average Molecular
Weight is almost always higher
than the Number Average
Molecular Weight ( ).
MOLECULAR WEIGHT
Molecular Weight
Just knowing the averages is
not enough, the
distribution of the
molecular weights also has
a large effect on how the
material will process and its
properties.
A broader or wide spec
distribution may make the
material unsuitable for
processes like injection
molding, but better suited
for processes like extrusion,
blow-molding, or
thermoforming.
Molecular Weight
For injection molding grades
of material, a narrower
distribution is better.
When the distribution is
narrow, the polymer
chains will melt and flow
at around the same
temperature.
The longer the chains, the
higher the viscosity or
resistance to flow.
Molecular Weight
When you have a broad or even a bi-
modal distribution, the shorter chains
melt more quickly and allow some
flow, while the longer chains hold the
material together.
This gives the polymer mixture melt
strength which allows it to be used
for some of the other processes
mentioned other than injection
molding.
Molecular Weight
You can have virtually an
infinite number or
distributions with the same
number average molecular
weight.

All of these materials will
process differently and have
at least slightly different
properties.
Properties
When making polymers, the goal is to make a material with the
ideal properties.

The longer the molecules (or the higher the molecular weight)
the higher the entanglement forces:
Longer hair is harder to get untangled than shorter hair
Properties
Increasing the molecular weight of the material increases many of
the properties of the material by increasing the entanglement of the
molecules.
A higher molecular weight:
Increases the chemical resistance - to a point
It takes more damage to the main chains of the molecules before
it will affect the strength of the material
The big loophole to this is if you have a chemical
that is very similar to the chemical makeup of the
main chain, it will dissolve it much more easily
Like Dissolves Like

Properties
A higher molecular weight:
Increases how far the material can stretch before rupturing
(ductility)
The higher degree of entanglement allows the material to
be pulled further before the chains break

Properties
A higher molecular weight:
Increases ductility: A candle and Polyethylene (PE) have
basically the same molecular structure. The chain length of
the candle is just much shorter than that of the PE. If you
bend a bar of PE in half it will bend, if you bend a candle in
half, it will fracture.

Properties
Processors want materials that will flow easily in order to form complex
geometries, but that can affect the properties of material used to create the
product.

Many times it turns out to be a trade-off between the required properties and
processability of the material.

CDs and DVDs are made from the same material as most safety glasses,
Polycarbonate.

Safety glasses require a higher molecular weight in order to provide the
necessary property of impact resistance.
CDs and DVDs require a lower molecular weight material in order to fill out
the thin walls. CDs and DVDs can shatter, safety glasses dont.

Properties
Molecular weight
Physical and mechanical property
implications
of molecular weight and MWD
Characterization of MWD
Relate MWD information to perform characteristics
of the finished product.
Property/process parameters
Increase the
MW
Tensile strength increase
Impact strength increase
Brittleness decrease
Abrasion resistance increase
Melt viscosity increase
Processing temperature increase
Molecular weight (cont.)

Measurement of MW
Primary methods to obtain absolute values of molecular
weight. Accurate but time consuming technique.
Osmetry (M
n
)
Scattering (M
w
)
Sedimentation (M
z
)
Secondary methods requires prior determination of empirical
relationships that relate the molecular weight to the viscosity of
a polymer solution or to the retention volume of polymer solution
being eluted from a gel permeation column. Its fast, simple &
accurate.
Intrinsic viscosity
GPC
Gel Permeation
Chromatography Theory
Used to separate liquid phase components
Form of size exclusion chromatography where small MW components
trapped in gel, higher MW components too large, pass around, come
out faster
Can estimate MW of unknowns by running standards of known MW
ELUTION VOLUME (mls)
16 18 20 22 24 26 28
Mw = 124600, Mn = 33200, MWD = 3.8
Mw = 73800, Mn = 37400, MWD = 2.0
Increasing Molecular Weight
* Trademark of The Dow Chemical Company
Molecular Weight Distribution Comparison
by Gel Permeation Chromatography
Properties: Molecular weight
synthetic polymers possess a molecular
weight distribution
39
M
i

N
i


M
w
=
N
i
M
i
2
i

N
i
M
i
i


M
n
=
N
i
M
i
i

N
i
i

polydispersity index = M
w
/M
n

Molecular weight and dispersion
Synthetic polymers always show a distribution in
molecular weights.
number average :


weight average:


(n
i
and w
i
are number and weight fractions, respectively,
of molecules with molar mass M
i
)

The polydispersity index is given by M
w
/M
n

=
i
i i
n
n
M n
M

= =
i i
i i i
i
i i
w
M n
M M n
w
M w
M
Molecular weight and dispersion -
an example:
Here are:
10 chains of 100 molecular weight
20 chains of 500 molecular weight
40 chains of 1000 molecular weight
5 chains of 10000 molecular weight
1347
5 40 20 10
) 10000 5 ( ) 1000 40 ( ) 500 20 ( ) 100 10 (
M
n
=
+ + +
+ + +
=
5390
) 10000 5 ( ) 1000 40 ( ) 500 20 ( ) 100 10 (
) 10000 5 ( ) 1000 40 ( ) 500 20 ( ) 100 10 (
M
2 2 2 2
w
=
+ + +
+ + +
=
4
M
M
sity Polydisper
n
w
~ =
What the Weights Mean
M
n
: This gives you the true average weight
Let's say you had the following polymer sample:
2 chains: 1,000,000 Dalton 2,000,000
5 chains: 700,000 Dalton 3,500,000
10 chains: 400,000 Dalton 4,000,000
4 chains: 100,000 Dalton 400,000
2 chains: 50,000 Dalton 100,000
10,000,000
10,000,000/23 = 435,000 Dalton

1 Dalton = 1 g/mole
Weight Average Molecular Weight
M
w
: Since most of the polymer mass is in the heavier fractions, this gives
the average molecular weight of the most abundant polymer fraction by
mass.

2,000,000
10,000,000
= 0.201,000,000 = 200,000
3,500,000
10,000,000
= 0.35 700,000 = 245,000
4,000,000
10,000,000
= 0.40 400,000 = 160,000
400,000
10,000,000
= 0.04100,000 = 4,000
100,000
10,000,000
= 0.01 50,000 = 500
Total = 609,500
Examples
Light scattering: larger molecules scatter more light than smaller ones.

Infrared absorption properties: larger molecules have more side
groups and light absorption (due to vibrational modes of side groups)
varies linearly with number of side groups.
Molecular Weights
Why do we care about weight average MW?
-some properties are dependent on MW (larger MW polymer chains can
contribute to overall properties more than smaller ones).
Distribution of
polymer weights
Polydispersity and Degree of Polymerization
Polydispersity:


M
w
M
n
>1
When polydispersity = 1, system is monodisperse.
Degree of Polymerization:


n
n
=
M
n
m
o
Number avg degree of polymerization


n
w
=
M
w
m
o
Weight avg degree of polymerization
Compute the number-average degree of polymerization for polypropylene,
given that the number-average molecular weight is 1,000,000 g/mol.


What is mer of PP?


Mer molecular weight of PP is
Example 1
C
3
H
6

m
o
=3A
C
+6A
H
=3(12.01 g/mol)+6(1.008 g/mol)
= 42.08 g/mol
Number avg degree of polymerization


n
n
=
M
n
m
o
=
10
6
g /mol
42.08g /mol
= 23,700
Problem 1 (a, b, and c)
A. Calculate the number and weight average degrees of polymerization
and polydispersity for a polymer sample (PP) with the following
distribution.
Avg # of monomers/chain Relative abundance
10 5
100 25
500 50
1000 30
5000 10
50,000 5
Problem 2 (b)
B. If the polymer is PMMA, calculate number and weight average
molecular weights.
M
w
if monomer is methylmethacrylate (5C, 2O, and 8H)
So m
0
= 5(12)+2(16)+8(1)= 100 g/mol
CH3
|
-CH2-C-
|
CO2CH3
Problem 3 (c)
C. If we add polymer chains with avg # of monomers = 10 such that their
relative abundance changes from 5 to 10, what are the new number
and weight average degrees of polymerization and polydispersity?
Add 5 more monomers of length 10 .
Regularity and symmetry of side groups affect properties
Stereoisomerism: (can add geometric isomerism too)
Polymer Molecular Configurations
Isotactic
On one side
Syndiotactic
Alternating sides
Atactic
Randomly placed
- Conversion from one stereoisomerism to another is not possible by simple
rotation about single chain bond; bonds must be severed first, then reformed!
Polymerize
Can it crystallize?
Melting T?
Regularity and symmetry of side groups affect properties
Polymer Geometrical Isomerism
cis-structure trans-structure

with R= CH
3
to form rubber
Cis-polyisoprene trans-polyisoprene
H H
-Conversion from one isomerism to another is not possible by simple
rotation about chain bond because double-bond is too rigid!

-See Figure 4.8 for taxonomy of polymer structures
Covalent chain configurations and strength:
Direction of increasing strength
Adapted from Fig. 14.7, Callister 6e.
Polymer Microstructure
Van der Waals, H
More rigid
Short branching
Long branching
Star branching
Dendrimers
Random, Alternating, Blocked, and Grafted
CoPolymers
Synthetic rubbers are often copolymers.

e.g., automobile tires (SBR)
Styrene-Butadiene Rubber random polymer
Example 3
Nitrile rubber copolymer, co-poly(acrylonitrile-butadiene), has



Calculate the ratio of (# of acrylonitrile) to (# of butadiene).


M
n
= 106,740 g /mol


n
n
= 2000
3 C = 3 x 12.01 g/mol
3 H = 3 x 1.008 g/mol
1 N = 1 x 14.007 g/mol

m
1
= 53.06 g/mol
4 C = 4 x 12.01 g/mol
6 H = 6 x 1.008 g/mol

m
2
= 54.09 g/mol
1,4-addition product


m
o
=
M
n
n
n
=
106,740
2000
= 53.57g /mol
We need to use an
avg. monomer MW:


m
o
=f
1
m
1
+f
2
m
2
=f
1
(m
1
m
2
) +m
2


f
1
=
m
0
m
2
m
1
m
2
=
53.37 54.09
53.06 54.09
= 0.7


f
2
=1f
1
= 0.3


f
2
f
1
=
0.7
0.3
7 : 3
Crosslinking in elastomers is called vulcanization, and is achieved by
irreversible chemical reaction, usually requiring high temperatures.
Vulcanization
Sulfur compounds are added to form chains that bond adjacent
polymer backbone chains and crosslinks them.
Unvulcnaized rubber is soft and tacky an poorly resistant to wear.
e.g., cis-isoprene
Stress-strain curves
+ (m+n) S
(S)
n

(S)
m

Single bonds
Double bonds
See also sect. in Chpt. 8
Molecular weight, Mw: Mass of a mole of chains.
Tensile strength (TS):
--often increases with Mw.
--Why? Longer chains are entangled (anchored) better.
% Crystallinity: % of material that is crystalline.
--TS and E often increase
with % crystallinity.
--Annealing causes
crystalline regions to grow.
% crystallinity increases.
crystalline
region
amorphous
region
Adapted from Fig. 14.11, Callister 6e.
Molecular Weight and Crystallinity
Polymer Crystallinity
polyethylene
Some are amorphous.
Some are partially crystalline (semi-crystalline).
Why is it difficult to have a 100% crystalline polymer?
%crystallinity =

c
(
s

a
)

s
(
c

a
)
100%

s
= density of specimen in question

a
= density of totally amorphous polymer

c
= density of totally crystalline polymer


%crystallinity =
M
crystalline
M
total
100%=

c
V
c

s
V
s
100%=

c

s
f
c
100%
Volume fraction of crystalline component.


M
total
=M
crystalline
+M
amophous
M
s
=M
c
+M
a

s
V
s
=
c
V
c
+
a
V
a

s
=
c
V
c
V
s
+
a
V
a
V
s
=
c
f
c
+
a
f
a
=
c
f
c
+
a
(1f
c
) =f
c
(
c

a
) +
a
Using definition of volume fractions:


f
c
=
V
c
V
s

f
a
=
V
a
V
s


f
c
=

s

a

c

a
Substituting in f
c
into the original definition:
%crystallinity =

c
(
s

a
)

s
(
c

a
)
100%
Polymer Crystallinity
Degree of crystallinity depends on processing conditions (e.g.
cooling rate) and chain configuration.

Cooling rate: during crystallization upon cooling through MP,
polymers become highly viscous. Requires sufficient time for
random & entangled chains to become ordered in viscous liquid.

Chemical groups and chain configuration:
More Crystalline
Smaller/simper side groups
Linear

Isotactic or syndiotactic
Less Crystalline
Larger/complex side groups
Highly branched
Crosslinked, network
Random
Semi-Crystalline Polymers
Fringed micelle model: crystalline region embedded in amorphous region.
A single chain of polymer may pass through several crystalline regions as
well as intervening amorphous regions.


f
c
=

s

a

c

a
Crystalline volume fractions Important
Thermoplastics:
--little cross linking
--ductile
--soften w/heating
--polyethylene (#2)
polypropylene (#5)
polycarbonate
polystyrene (#6)
Thermosets:
--large cross linking (10 to 50% of mers)
--hard and brittle
--do NOT soften w/heating
--vulcanized rubber, epoxies,
polyester resin, phenolic resin
Callister,
Fig. 16.9
T
Molecular weight
T
g
T
m
mobile
liquid
viscous
liquid
rubber
tough
plastic
partially
crystalline
solid
crystalline
solid
Adapted from Fig. 15.18, Callister 6e.
Thermoplastics vs Thermosets
T
m
: melting over wide range of T
depends upon history of sample
consequence of lamellar structure
thicker lamellae, higher T
m
.
T
g
: from rubbery to rigid as T lowers
Packing of spherical atoms as in ionic and metallic crystals led to
crystalline structures.

How polymers pack depend on many factors:
long or short, e.g. long (-CH
2
-)
n
.
stiff or flexible, e.g. bendy C-C sp
3
.
smooth or lumpy, e.g., HDPE.
regular or random
single or branched
slippery or sticky, e.g. C-H covalent (nonpolar) joined via vdW.

Analogy: Consider dried (uncooked) spaghetti (crystalline) vs.
cooked and buttered spaghetti (amorphous).
pile of long stiff spaghetti forms a random arrangement.
cut into short pieces and they align easily.

Candle wax more crystalline than PE, even though same chemical
nature.
Packing of Polymers
Would you expect melting of nylon 6,6 to be lower than PE?
What Are Expected Properties?

N
|
H

H
|
C
|
H








(

(
(
(
(
(
(
6

N
|
H

O
||
C

H
|
C
|
H








(

(
(
(
(
(
(
4

N
|
H

O
||
C

N
|
H

H
|
C
|
H








(

(
(
(
(
(
(
6

N
|
H

O
||
C

H
|
C
|
H








(

(
(
(
(
(
(
4

N
|
H

O
||
C

+
+
+
+
+
+

H
C
H

H
C
H

H
C
H

H
C
H

+
+
+
+
+
+
nylon 6,6
polyethylene
a) What is the source of intermolecular cohesion in Nylon vs PE?
b) How does the source of linking affect temperature?
Hydrogen bonds
Van der Waals bonds
With H-bonds vs vdW bonds, nylon is expected to have (and does) higher melting T.
Which polymer more likely to crystallize? Can it be decided?
What Are Expected Properties?
Linear syndiotactic polyvinyl chloride
Linear isotactic polystyrene
Linear and syndiotactic polyvinyl chloride is more likely to crystallize.
The phenyl side-group for PS is bulkier than the Cl side-group for PVC.
Generally, syndiotactic and isotactic isomers are equally likely to crystallize.
For linear polymers, crystallization is more easily accomplished as chain
alignment is not prevented.
Crystallization is not favored for polymers that are composed of
chemically complex mer structures, e.g. polyisoprene.
Which polymer more likely to crystallize? Can it be decided?
What Are Expected Properties?
Linear and highly crosslink
cis-isoprene
Not possible to decide which might crystallize. Both not likely to do so.
Networked and highly crosslinked structures are near impossible to
reorient to favorable alignment.
H
+
+ H
2
0
Networked
Phenol-Formaldehyde
(Bakelite)
Polymer Microstructure
Polyolefins with side chains have stereocenters on every other carbon
CH
3
n
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
With so many stereocenters, the stereochemistry can be complex. There
are three main stereochemical classifications for polymers.
Atactic: random orientation
Isotactic: All stereocenters have same orientation
Syndiotactic: Alternating stereochemistry
Tacticity
Tacticity stereoregularity of chain
C C
H
H
H
R R
H
H
H
C C
R
H
H
H
C C
R
H
H
H
C C
C C
H
H
H
R
C C
H
H
H
R
C C
H
H
H
R R
H
H
H
C C
C C
H
H
H
R R
H
H
H
C C
R
H
H
H
C C
R
H
H
H
C C
isotactic all R groups on
same side of chain


syndiotactic R groups
alternate sides


atactic R groups random
Why is this important?
Tacticity affects the physical properties
Atactic polymers will generally be amorphous,
soft, flexible materials
Isotactic and syndiotactic polymers will be
more crystalline, thus harder and less flexible
Polypropylene (PP) is a good example
Atactic PP is a low melting, gooey material
Isoatactic PP is high melting (176), crystalline,
tough material that is industrially useful
Syndiotactic PP has similar properties, but is
very clear. It is harder to synthesize

Linear polymers with side branches
Isotactic
Same side of the linear
polymer
Greater effect of dispersion
forces therefore high
density, rigid and tough
and a high softening temp.
Atactic
Irregular points on both
sides of the linear polymer
Chains of molecules cannot
get close together, therefore
low density.
Soft, waxy little use

Poly(propene)
This varying degree of randomness will affect the
strength and melting point of the polymer.

The less random, the stronger the polymer and the
higher the melting point

This is because in a more ordered polymer they
chains can get closer together and hence the van
der Waals forces will be greater.

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