Types of Polymers

• Polymer Classifications
– Thermoset: cross-linked polymer that cannot be
melted (tires, rubber bands)
– Thermoplastic: Meltable plastic
– Elastomers: Polymers that stretch and then return to
 Monomer
Common Polyolefins
Polymer
CH3
H3C
Polyethylene n
Ethylene Repeat unit

CH3
CH3 n
P o ly p ro p y le n e CH3 CH3 CH3 CH3 CH3 CH3 CH3
P ro p y le n e

C
H3
P
h n
P
oly
sty
ren
e P h P
h P h P
h P
h P
h P
h
S
ty
ren
e

C
H3
C
l n
P
ol
y(v
i
n y
lc
hl
o r
i
d e
) C
l C
l C
l C
l C
l C
l C
l
V
i
n y
lC
hl
o r
i
d e
F
2F2F2F2F2F2
FCCF CC C C C C C
F3
2 2 F
C C C C C C C
3 n
T
e
t
ra
f
lu
or
oe
t
hy
le
neP
ol
y(
te
t
ra
f
lu
or
oe
t
hy
le
ne
)
:T
ef
l
onF2F2F2F2F2F2
 Polyesters, Amides, and
Monomer Urethanes Polymer
O O
H2 H2
HO 2 C CO 2 H OH HO O C C O H
HO
Ethylene Poly(ethylene terephthalate n
Terephthalic
acid glycol Ester

O O O O
H
H O O H H 2N 4
N H 2 H O N N
4 4 4
A d ip ic A c id 1 ,6 - D ia m in o h e x a n e N y lo n 6 ,6 H H n
A m id e
O O
H H
H O 2C C O 2H H 2N N H 2 H O N N H
K e v la r n
T e r e p h th a lic 1 ,4 - D ia m in o
a c id b e n ze n e

H2
OCN NCO HO
C OH

Ethylene Spandex
4,4-diisocyantophenylmethane
glycol
O O
H H2 H H2 H2
HO N C N O C C O H Urethane linkage
n
 Polymer Synthesis
• 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
– 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
 Addition Polymerization
A
In* In A* A
Initiation
 Addition Polymerization
Propagation

A
I
n* I
nAA
* A
I
nit
iat
ion
 Addition Polymerization
Propagation

A
I
n* I
n A
AA*A
In
i
t
iat
i
on
 Addition Polymerization
A n
A
I
n* I
n AAAA
* I
nAA
A
AA
*
I
ni
ti
ati
on Pr
o
p
a
ga
t
i
o
n n

*A A A A A
A *
A AAAA m
m

I
nAAAAA In A A A A A A A A A A
In A A A A A n
n n m

A * Combination
BAAAA
m
C h a in T r a n s fe r D
i
spr
opo
r
ti
ona
t
ion
N e w r e a c tiv e s ite
is p r o d u c e d
T
e
r
m
i
n
at
i
o
n
R
e
a
c
t
i
v
es
i
te
i
s
co
ns
u
m
e
d
MW

k propagation
MW 
k ter mination

0 100
% conversion
 Types of Addition
Anionic
Polymerizations
n
Ph L i+ L i+
P h C 4H
C3H7 Li C 4H 9 9 n
Ph P h P h
R a d ic a l

n
Ph Ph
P h C O 2• P
hC
O2 PhCO2
n
P
h Ph Ph
Cationic

n
Ph Ph
Cl3Al OH H H H
OA
lC
l3
2 n
P h P
h P
h
HOA
lCl3
 Step-Growth Polymerization
Stage 1
n n
Consumption
of monomer

S ta g e 2

C o m b in a tio n
o f s m a ll fr a g m e n ts

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.
 Nylon-6,6
O O O O
N a O H
C l C l H 2 N N H 2
H
4 4 C l 4
N 4 N
H H
A d ip o y l c h lo r id e 1 ,6 - D ia m in o h e x a n e

O O
A d ip o y l c h lo r id e H
in h e x a n e H O N N
4 4
H H n
N y lo n 6 ,6
6 c a rb o n 6 c a rb o n
d ia c id d ia m in e
D ia m in e , N a O H , in H 2 O
N y lo n - 6 ,6
 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.

A d ip o y l c h lo r id e
in h e x a n e

N y lo n 6 ,6

D ia m in e , N a O H , in H 2 O
Molecular weight of
polymers
 MOLECULAR WEIGHT
• Molecular weight, M: Mass of a mole of chains.

Low M

high M

• Polymers can have various lengths depending on the number of repeat units.
• During the polymerization process not all chains in a polymer grow to the same
length, so there is a distribution of molecular weights. There are several ways of
defining an average molecular weight.
• The molecular weight distribution in a polymer describes the relationship between
the number of moles of each polymer species and the molar mass of that species.

15
 Polymer = Macromolecule
the high molecular weight is the principal characteristic,
which
1. distinguishes polymers from other chemical substances,
and
2. provides unique and diverse properties to polymeric
materials finding infinite applications in various areas of
human society
 From little molecules to big molecules
Effect on: 145 C for polyethylene

Melting temperature
1. melting point
2. the degree of polymer
H – (CH2)n – H
entanglement
3. the degree of
intermolecular interactions
Molecular weight

4. physical and mechanical

properties
5. tensile strength Tensile strength
6. melt-processing
conditions

7. application
Molecular weight
 Molecular weight of polymers
the properties to be known are:

 preparation method
 properties
 processing
 application
Number Average and Weight Average Molecular Weight

. The molecular weight of polymers

a. Some natural polymer (monodisperse) :

All polymer molecules have same molecular weights.

b. Synthetic polymers (polydisperse) :

The molecular weights of polymers are distributed

c. Mechanical properties are influenced by molecular weight

much lower molecular weight ; poor mechanical property
much higher molecular weight ; too tough to process
optimum molecular weight ; 105 -106 for vinyl polymer
15,000 - 20,000 for polar functional group containing polymer (polyamide)
 POLYMERS – Molecular Weight
• Degree of Polymerization (DP)

- Total number of repeat units (mers) or “n”

- Thus, DP is related to molecular weight

Here: DP of PS = 700
CH2 CH
700 Does every PS chain in a given sample contain exactly
700 repeat units?

No. On average, each PS is 700 repeat units in length

- Synthetic polymer chains within a given sample are of varying lengths

(i.e. have different DP’s and hence different MW’s)

-Thus, refer to “n” as “average degree of polymerization” or DP: “average

# of repeat units (mers) or “n”
 POLYMERS – Molecular Weight

CH2 CH
700 What is the MW of PS if n = 700?

MWpolymer = DP x MWmer MWpolymer = 700 x 104 g/mol = 72,800 g/mol

What is the DP of PS if MW = 200,000 g/mol ?

DP = MWpolymer / MWmer DP = 200,000 g/mol / 104 g/mol = 1923

(or “n” = 1923)
 POLYMERS – Molecular Weight
• Thus, samples of PS (and all other polymers) are “POLYDISPERSED”:
have a mixture of MW’s

• When the MW of a polymer sample is experimentally determined, an

“AVERAGE MW” will always be obtained.

• Two common “AVERAGE MW’s” are measured for polymers:

Mn or Number Average MW
Mw or Weight Average MW Mn
Mw
Mw > Mn

amount
FYI:
Techniques used to measure Mw: large chains
contribute more to measurement versus small chains

Techniques used to measure Mn: all chains

contribute equally to measurement MW
 wi = grams
Mn =  wi  Ni M i Ni = moles
 Ni
=
 Ni Mi = g/mol
wi = NiMi

Mw =  wi M i  Ni M i
2

 wi
=
 Ni M i

Consistency example
 Polydispersity Index (PDI)

PDI = Mw/Mn

- PDI > 1 (since Mw > Mn )

Close in value Mw >> Mn
Mn
Mw Mn
Mw
amount

amount

amount
MW MW MW

PDI = 1 PDI = 1.1 - ~1.3 PDI = 2-10

(proteins only) “narrow polydispersity” “broad polydispersity”
 What the Weights Mean
Mn: This gives you the true average weight.
If the molecular weight of the repeating unit is 90, calculate
the number of repeating units?

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
Number-average molecular weight (n)
Example - a polymer sample consists of 9
molecules of mw 30,000 and 5 molecules of mw

50,000
 M i Ni
(9  30,000)  (5  50,000)
Mn  i 1
  37,000
(9  5)
 Ni
i 1
Weight-average molecular weight (w)
Consider the previous example - 9 molecules of
molecular weight 30,000 and 5 molecules of molecular
weight 50,000

9(30,000) 2  5(50,000) 2
Mw   40,000
9(30,000)  5(50,000)
Polymer Properties

Glass Transition Temperature (Tg)

The temperature (actually a broad range of temperatures) at which a glassy polymer softens into a viscous liquid or
rubbery phase. On the molecular level, it is the temperature at which chains in amorphous (i.e., disordered) regions of
the polymer gain enough thermal energy to begin sliding past one another at a noticable rate. For an amorphous
polymer, the Tg reports the minimum processing temperature. The Tg is strongly dependant on polymer structure
(including stereochemistry), and ranges from far below 0 °C for very flexible chains, and above 400 °C for very stiff
chains.

The transition is detectable by a variety of methods, including Differential Scanning Calorimetry (DSC), and Thermal-
Mechanical Analysis (TMA). Note that some authors report the Tg as the onset temperature (i.e., the beginning of the
range), while others report the midpoint of the range.

Melting Temperature (Tm)

The temperature (actually a narrow range of temperatures) at which the ordered regions of a crystalline polymer melt,
similar to a small molecule. Crystallization is essential for many high-performance polymers because it greatly
increases the strength of the material.
Like the Tg, the Tm is detectable by DSC, TMA, and other techniques.

Decomposition Temperature
The temperature above which chemical degradation occurs.

This temperature is conveniently measured by Thermogravimetric Analysis (TGA), a technique in which one simply
weights the sample continuously while heating it. Once decomposition begins, small molecular fragments are released
which distill away, and the sample loses weight.

Modulus
The proportionality constant between stress and strain, and therefore can be thought of as stiffness.
Dependance of Polymer Properties on MW
Many polymer properties of interest (Tg, modulus, tensile strength, etc.) follow a
peculiar pattern with increasing MW. Small molecules have small values, then there
is a sharp rise in properties as the chains grow to intermediate size (oligomers), and
then the properties level off as the chains become long enough to be true polymers.

However, a few properties important

for polymer processing, like melt
viscosity and solution viscosity,
increase monotonically with MW. This
means that the goal of polymer
synthesis is not to make the largest
possible molecules, but rather, to
make molecules large enough to get
onto the plateau region. Increasing the
MW beyond this does not improve the
physical properties much, but makes
processing more difficult.
A few properties are dictated by the
repeat units alone, and therefore these
are not changed much by MW.
Examples: color, dielectric constant,
and refractive index.