Part I: POLYMER CHEMISTRY

Chapter 3: Molar mass & Degree of Polymerization

 MOLECULAR WEIGHT
1. Of homopolymer:
M = xM 0
M0: molecular weight of 1 repeating unit
2. Of copolymer:
M = xM 0cop với M 0cop = ∑ X j M 0j
X j , M 0j : mole fraction, unit number “j”
 AVERAGE MOLECULAR WEIGHT
3. Number average molecular weight (M n ):
- is defined as the sum of the products of the molar mass of
each fraction multiplied by its mole fraction
(1)
Mn = ∑ XiMi

where X i is the mole fraction of molecules of molar mass

M i is given by the ratio of Ni to the total number of
molecules. Therefore it follows that
∑ Ni M i (2)
Mn =
∑ Ni
 AVERAGE MOLECULAR WEIGHT
Ex1: Given Polymer molecular weight distribution,
calculate number average molecular weight.
Mi (kg/mol) Xi
14 0.05
26 0.15
38 0.21
50 0.28
62 0.18
74 0.10
86 0.03
 AVERAGE MOLECULAR WEIGHT
- The weight fraction wi is defined as the mass of molecules of
molar mass Mi divided by the total mass of all the molecules
Ni M i
present wi = (3)
∑ Ni M i
wi Ni
= (4)
M i ∑ Ni M i
Thus,
 wi  ∑ Ni (5)
∑ =
 M i  ∑ Ni M i
Therefore
∑ Ni M i 1 (6)
Mn = =
∑ Ni ∑ ( wi / M i )
 AVERAGE MOLECULAR WEIGHT
4. Weight-average molar mass ( M w):
- is defined as the sum of the products of the molar mass of
each fraction multiplied by its weight fraction
M w = ∑ wi M i (7)
where Ni M i
wi =
∑ Ni M i (8)

2
Thus ∑ Ni M i (9)
M w = ∑ wi M i =
∑ Ni M i
 AVERAGE MOLECULAR WEIGHT
Ex2: Given Polymer molecular weight distribution,
calculate weight average molecular weight.
Mi (kg/mol) Xi
14 0.05
26 0.15
38 0.21
50 0.28
62 0.18
74 0.10
86 0.03
 AVERAGE MOLECULAR WEIGHT
5. Polydispersity index (PDI))
Mw (10)
PDI =
Mn
6. Viscosity Average Molecular Weight (M v )
The molecular weight of the polymer is measured by using
viscometer and the molecular weight obtained by this
technique is called viscosity average molecular weight.
 AVERAGE MOLECULAR WEIGHT
Ex3: Calculate PDI of polymer given in Ex1.

Mi (kg/mol) Xi
14 0.05
26 0.15
38 0.21
50 0.28
62 0.18
74 0.10
86 0.03
METHODS TO DETERMINE
AVERAGE MOLECULAR WEIGHT OF POLYMER

• Vapour Pressure Osmometry

• Ebulliometry and Cryosscopy
• End group analysis
Mn

• Light scattering

Mw • Gel Permeation Chromatography (GPC)

• Viscosity
Mv
 Determination of
Viscosity Average Molecular Weight

Principle:

Polymer with Polymer with

higher molecular weight lower molecular weight

higher viscosity lower viscosity

 Determination of
Viscosity Average Molecular Weight

Mark – Houwink – Sakurada equation:
the relationship among the molecular weight and
viscosity are given
[η ] = KM α
K,α: constants for a particular polymer solvent system
+ polymer
+ solvent
+ temperature

η]) ???
How to determine ([η
 Determination of
Viscosity Average Molecular Weight

Poiseuille’s law – the relationship among viscosity (h)
and time:
π .P.r 4 π .g.H .d .r 4
η= .t = .t = K .d .t
8 LV 8 LV
L, r: length, radius of the capillary tube
P = g.H.d: pressure suất, gravity acceleration, capillary
solution level difference and solution density
t: time for V(l) liquid flow
K: constant of the viscometer

Viscosity is proportional to time.

 Determination of
Viscosity Average Molecular Weight
 Theory
η r)
 Relative viscosity (η
η solution t
ηr = =  Huggins equation
η solvent t0 ηsp
= [η ] + kH [η ] C
2
ηred =
 Specific viscosity (η ηsp) C
t − t0
η sp = = ηr − 1
t0
η])
Intrinsic viscosity ([η
ηred)
 Reduced viscosity (η
η sp η sp
ηred = [η ] = Clim
→0
(*)
C
C
 Determination of
Viscosity Average Molecular Weight
 Theory
η r)
 Relative viscosity (η
η solution t
ηr = =  Kraemer equation
η solvent t0
ln (ηred )
ηsp) = [η ] + k K [η ] C
2
 Specific viscosity (η
t − t0 C
η sp = = ηr − 1
t0
Intrinsic viscosity
ηred)
 Reduced viscosity (η ln(ηred )
η sp [η ] = Clim (**)
ηred = →0 C
C
 Determination of
Viscosity Average Molecular Weight

 Huggins equation  Kraemer equation

ηsp
= [η ] + kH [η ] C ln (ηred )
2
ηred =
= [η ] + k K [η ] C
2
C
C

η])
Intrinsic viscosity ([η Intrinsic viscosity
η sp ln(ηred )
[η ] = Clim (*) [η ] = Clim
→0 (**)
→0 C C
 Determination of
Viscosity Average Molecular Weight
 Data analysis  Plotting

η])

Intrinsic Viscosity ([η
 Huggins equation
ηsp
= [η ] + kH [η ] C (*)
2
ηred =
C
 Kramer equation
η]
[η
ln (η red )
= [η ] + k K [η ] C (**)
2

η])
Determine intrinsic viscosity ([η
Determine viscosity average molecular weight of polymer
 Determination of
Viscosity Average Molecular Weight
 Experiment

Viscometer

Ostward U-tube viscometer Ubbelohde viscometer

 Determination of
Viscosity Average Molecular Weight

Apparatus:
 Determination of
Viscosity Average Molecular Weight

Tools:
Chemicals:
- Stopwatch - Solvent
- Pipette - Polymer to determine
- Scale the average molecular
- Beaker weight
- Stirrer
- Cylinder
- Funnel
- Thermometer
- Thermostat water
bath
METHODS TO DETERMINE
AVERAGE MOLECULAR WEIGHT OF POLYMER

• Vapour Pressure Osmometry

• Ebulliometry and Cryosscopy
• End group analysis
Mn

• Light scattering

Mw • Gel Permeation Chromatography (GPC)

• Viscosity
Mv
 Gel Permeation Chromatography (GPC)

Principle:
- GPC is a form of size-exclusion chromatography in which
the polymer molecules elute from the chromatography
column in order of decreasing molecular size in solution.
- Separation occurs via the use of porous beads packed in
a column

Schematic of pore vs. analyte size

 Gel Permeation Chromatography (GPC)

Principle:

Flow in column
 Gel Permeation Chromatography (GPC)

Principle:

Flow of polymer solution

 Gel Permeation Chromatography (GPC)

Apparatus:
Gel Permeation Chromatography (GPC)

Tool:
Chemicals:
- Pump - Tetrahydrofuran (THF)
- Chromatographic - Polymer to determine
column the average molecular
- Beads weight
- UV/IR detector
- Syringe
Gel Permeation Chromatography (GPC)

Molecular weight
Calibration
Polymer solution

Time Mw
Molecular c
Mz
weight Mn
c
fraction

Time

Concentration of solution via time

 Gel Permeation Chromatography (GPC)

Advantages:
- Short analysis time.
- Well defined separation.
- Narrow bands and good sensitivity.
- The small amount of mobile phase
required.
- The flow rate can be set.

Disadvantages:
- Standard sample is required.
- GPC is expensive.

PL-GPC 50
Part I: POLYMER CHEMISTRY

Chapter 4: Principles of Polymerization

 Introduction
1. Basic requirement for polymerization
- each molecule of monomer must be capable of being
linked to two (or more) other molecules of monomer by
chemical reaction, i.e. monomers must have a functionality
of two (or higher).

the number of different synthetic polymers that have

been prepared is extremely large and many can be formed
by more than one type of polymerization.
 Classification
1. Carothers method: is based upon comparison of the
molecular formula of a polymer with that of the monomer(s)
from which it was formed
2 types
- Addition polymerization
- Condensation polymerization
2. Modern method: is based on polymerization mechanism
2 types
- Chain-growth polymerization
- Step-growth polymerization
 Classification

Formation of Chain-growth polymerization Step-growth polymerization

Dimer I + o  I-o o + o  o-o
I-o + o  I-o-o
Trimer I-o-o + o  I-o-o-o o-o + o  o-o-o
Tetramer I-o-o-o + o  I-o-o-o-o o-o-o + o  o-o-o-o
o-o + o-o  o-o-o-o
Pentamer I-o-o-o-o + o  I-o-o-o-o-o o-o-o-o + o  o-o-o-o-o
o-o + o-o-o  o-o-o-o
Hexamer I-o-o-o-o-o + o  I-o-o-o-o-o-o o-o-o-o-o + o  o-o-o-o-o-o
o-o-o + o-o-o  o-o-o-o-o-o
o-o + o-o-o-o  o-o-o-o-o-o
 Classification
Chain-growth Step-growth polymerization
polymerization
Reacting - Monomer - Monomer with functional group
agents
- Initiator
- Active centers are formed - Reaction occur between two
from the initiators molecules with functional group
- Monomer reacts with active
center forming new active
center
- Propagation involves growth
of a chain by addition of a
monomer to the active center
- Reaction only occurs between - Reaction occur between any
monomer and active center molecules (monomer, dimer,
trimer) with functional group
- Monomer participates in the - Most of monomers participate
reaction during the process. in the early stage of the reaction.
 Classification
Chain-growth Step-growth polymerization
polymerization
Average - Hight average molecular - Average molecular weight
molecular increases with reaction time.
weight is form at the early
weight
stage of the reaction
Yield - Depends on the mechanism - Almost unchanged.
Component of - Only polymer and forming - All types of products
mixture product