Manual Fu

Basic Laboratory Course
for
Polymer Science M. Sc. Program

POLYMER SYNTHESIS AND
CHARACTERIZATION

Department of Biology, Chemistry and Pharmacy
Free University Berlin
November, 2001

i
CONTENTS

1
1
8

14
14
20

23
23
24

27
27
32

34

43

45

48
CHAIN-GROWTH POLYMERIZATION
Section 1 Free Radical-Chain Growth Polymerization
1.1 Introduction
1.2 Experiments
E1.1 Bulk Polymerization of MMA with AIBN (Trommsdorff-Norrish Effect)
E1.2 Suspension polymerization of Styrene with Dibenzoyl Peroxide
E1.3 Dilatometry
Section 2 Anionic Polymerization
2.1 Introduction
2.2 Experiments
E2.1 Synthesis of Isotactic and Syndiotactic Poly (methyl methacrylate)
E2.2 Determination of the Ceiling Temperature of -Methylstyrene
Section 3 Copolymers
3.1 Introduction
3.2 Experiments
3.2.1 Statistical Copolymerization
E3.1.1 Free Radical Copolymerization of Styrene and MMA
E3.1.2 Anionic Copolymerization of Styrene and MMA
E3.1.3 Cationic Copolymerization of Styrene and MMA

3.2.2 Block Copolymerization
E3.2.1 Anionic Block Copolymerization of Styrene and MMA
E3.2.2 Anionic Homopolymerization of Styrene

Section 4 Insertion Polymerization
4.1 Introduction
4.2 Experiments
E4.1 Synthesis of high syndiotactic ploy (styrene) by homogeneous Ziegler-Natta catalysts
E4.2 Ring Opening Metathesis Polymerization (ROMP) of Norbornene

STEP-GROWTH POLYMERIZATION
Section 5 Polycondensation
E5.1 Synthesis of Unsaturated Polyester
E5.2 Synthesis of Nylon 6,6 by Melt Polycondensation
E5.3 Interfacial Polycondensation of Hexamethylenediamine and Sebacoyl Chloride
E5.4 Synthesis of Liquid Crystalline Main Chain Polymer by Interfacial Polycondensation

Section 6 Polyaddition
E6.1 Synthesis of Polyurethane Foams
E6.2 Synthesis of polyurethane elastomer

REACTIONS OF POLYMERS
Section 7 Cross-Linking Reactions
E7.1 Synthesis of Ion Exchanging Resin
E7.2 Synthesis of Photoresist and Photolytic Crosslinking
E7.3 Synthesis of Boron Containing Siloxane

POLYMER CHARACTERIZATION
Section 8 Polymer Characterization
E8.1 Characterization of Copolymers from E3.1.1 to 3.1.3 by IR, NMR, and GPC
E8.2 Dilute Solution Viscosity

Appendix A Order of Experiments
Appendix B List of Chemicals
Appendix C List of Glassware
Appendix D Safety Rules

Section 1 Free Radical Chain Growth Polymerization Introduction
1
Section 1 Free Radical-Chain Growth Polymerization

1.1 Introduction

Free radical chain polymerization is by far the most commonly used method in industry to manufacture
polymers. The three polymers of major economic importance low-density polyethylene (PELD), polystyrene
(PS), and ploy (vinyl chloride) (PVC) - are manufactured by free radical polymerization. Further more,
ploy(vinyl acetate) (PVAC), ploy(methyl methacrylate) (PMMA), ploy(acrylonitrile) (PAN) and many other
polymers or copolymers also come from free radical polymerization.

With some exceptions (such as propellanes), free radical polymerization is restricted to unsaturated organic
compounds, and normally olefins. Since every monomer is added to the chain end, it is a chain-growth
polymerization process.

R
R R R
(1.1)

There is a great variety of process for free radical polymerization. The polymerization system could be
homogeneous or heterogeneous, and the polymerization could be carried out in bulk, solution, suspension, or
emulsion et al.

1.1.1 Kinetics of free radical polymerization

Like most other free radical reactions of low molecular compounds (for example halogenation), free radical
polymerization is a chain reaction and can be divided into four parts:

- Initiation
- Propagation
- Transfer Reactions
- Termination

Each step may have a significant influence on the choice of polymerization conditions and the properties of the
polymer.

1.1.1.1 Initiation

The initiation reaction is the attack of a monomer (M) molecule by a primary radical
0
R
&
originated from the
initiator (I). This process involves two reactions:

Decomposition of the initiator to form primary radicals

0
k
R 2
d &
I
The actual initiation reaction

1 o
R M R
& &
+

The initiator decomposes in an unimolecular reaction into two initiator radicals with a rate constant k
d
.

Reaction rate:
dt
] R [ d
2
1
] I [ k
dt
] I [ d
0
d
&
(1.2)

The time dependence of the initiator concentration could be obtained by integration of equation (1.2)

2
t -k
0
d
e ] I [ ] I [ (1.3)

If half-life time of the initiator is long compared to the duration of the polymerization process (decomposition of
the initiator is the rate determining step), the initiator concentration can be assumed to be constant.
In this case the reaction rate of the initiation reaction can be written as:

] I [ f k 2
dt
] R [ d
V
d
1
d

&
(1.4)

In this equation
1
R
&
means the radicals that are able to propagate and f is the probability factor for a primary
radical to undergo reaction with a monomer M rather than to combine with another radical and form a unreactive
product.

1
generated radicals
radicals staring" "
f (Usually in the range of 0.5-0.8)

1.1.1.2 Propagation

The propagation reaction is characterized by the consumption of one radical to form another radical.

In the propagation process, a monomer molecule is taken up by the primary radical to form a new radical with
the rate constant k
P1
. This new radical takes up another monomer molecule to form a new radical with the rate
constant k
P2
etc.

.
.
.
R M R
R M R
3
k
2
2
k
1
Pr2
Pr1
& &
& &
+
+

With the assumption that all radicals R
i
have the same reactivity, the k
Pr
s are the same for all chain lengths.

This leads to the rate of the propagation reaction as:

][M] R [ k
dt
] [M d
V
Pr Pr
&
(1.5)

whereR
&
represents the sum over all growing polymer radicals with degree of polymerization i ( ] R [ R
i
i
& &
).

1.1.1.3 Transfer reactions

Transfer reactions have the same characteristic as the propagation reaction, in which one radical is consumed
when another is formed. The difference is in the nature of the new radical. During propagation the new radicals
are polymer radicals with one repeating unit ( RU) more than the original, while the radicals formed in a transfer
reaction may be a monomer radical or a substrate radical.

Example: Self-inhibition of allylic monomers (transfer to monomers)

R
Cl Cl Cl
n
Cl
R
Cl Cl Cl
n
Cl
(1.6)

3

M P M R
i
k
i
f & &
+ + (1.7)

The rate of the transfer reaction to the monomer can be written as:

] R M][ [ k
dt
[M] d
V
f f
&
(1.8)

The monomer radical can than start a new chain. This is called reinitiation by transfer radicals.

2
k
R M M
PM & &
+ (1.9)

In this case k
PM
= k
P
. Therefore the rate of polymerization is not influenced by the transfer reaction, but the
degree of polymerization may decrease dramatically.

1.1.1.4 Termination

A termination reaction normally involves two radicals, reacting either by recombination or by
disproportionation.

Recombination means the formation of a single bond between two polymer radicals leading to an unreactive
polymer molecule of on an average twice the size of the polymer radicals.

m n
k
m n
P R R
t
+
+
& &
(1.10)

Recombination broadens the molecular weight distribution, thus increases the polydispersity.

Disproportionation means the hydrogen transfer from one polymer radical to the other, whereby one of the
unreactive polymer molecules is saturated and the other involves a terminal double bond.

R R R R
(1.11)

Kinetically both types of termination are identical. The rate of consumption of growing radicals is given by:

2
t t
] R [ k
dt
] R [ d
V
&
&
(1.12)

1.1.1.5 Rate of polymerization

In order to obtain the total rate of polymerization from the rate equations above, the steady-state assumption is
made, which means, after a short initiation time the number of growing radicals is constant, i.e., the rate of
initiation (equation 1.4) is equal to the rate of termination (equation 1.12).

] I [ f k 2 ] R [ k
d
2
t

&
(1.13)
The assumption is reasonable, because an excess of termination would stop the polymerization very fast and an
excess of initiation leads to the Trommsdorf-Norrish effect (see below).

Equation (1.13) can be solved for [ R
&
], the concentration of growing radicals:

4
2
1
t
d
k
] I [ f k 2
] R [
(
(
,
\
,
,
(
j
&
(1.14)

Introducing this equation into equation (1.5), one can obtain the general equation for the rate of polymerization:

[I] ] M [ k ] M [
k
] I [ f k 2
k
dt
] M [ d
V
Poly
2
1
t
d
Pr Poly

(
(
,
\
,
,
(
j
(1.15)

The polymerization rate is half as much as the initiator concentration.

The assumptions underlying this calculation are:

KPr is independent of the length of the growing chain.
The concentration of the active sites is constant, which implies that the initiator concentration stays the
same. Therefore, the validity of this assumption is limited to processes that are as short as the half-life time
of the initiator. Otherwise, the initiator consumption has to be taken into account in equation (1.15) by
introducing equation (1.3).

1.1.2 Kinetic chain length and average degree of polymerization

The kinetic chain length is defined as the average number of growth steps per effective free radical until its
termination, which is given by the ratio of propagation rate to initiation rate (= termination rate).

t
Pr
d
Pr
V
V
V
V
(1.16)

In the case of the absence of transfer reactions and termination exclusively by disproportionation, the kinetic
chain length is equal to the number average degree of polymerization.

n
P (1.17)

In the case of the absence of transfer reactions and termination exclusively by recombination, the number
average degree of polymerization is twice the value of
2 P
n
(1.18)

In a normal polymerization process, these two termination ways coexist.

1 a 2 1 a 2 P
n
(1.19)

The parameter a describes the proportion of chains which have undergone termination by recombination.

The dependence of the number average degree of polymerization on the initiator and monomer concentration can
be derived from equations (1.16, 1.4, and 1.5).

(
(
(
,
\
,
,
,
(
j
2
1
t d
Pr
n
]) I [ fk k 2 (
] M [ k
a 2 P (1.20)

The degree of polymerization decreases with the initiator concentration and increases with the monomer
concentration.

1.1.3 Influence of transfer reactions to the degree of polymerization

5
If transfer reactions occur to monomers, the kinetic chain length, is not influenced, because it is assumed that
the rate constants for the polymer chain and the reinitiated polymer chain are equal, and also because of the
definition of the kinetic chain length (1.3). But the degree of polymerization is obviously influenced by transfer
reactions.

A definition of the degree of polymerization is given by equations (1.10) and (1.11):

unit per time molecules polymer produced of number
unit per time monomers consumed of number
n
P

Transfer reactions increase the number of polymer molecules and therefore decrease the degree of
polymerization. (For a more elaborate derivation see the literature.)

1.1.4 Trommsdorf-Norrish effect

The statements made so far refer to ideal kinetics of the polymerization system at low (but not too low)
conversions. While at very low conversions, the polymerization rate should increase for a short time until the
stationary state is reached (non-stationary initiation phase) as shown in Fig. 1.1.

Fig. 1.1 Plot of the rate of polymerization versus conversion: n-stat = non-stationary state, stat =
stationary state; ideal = ideal kinetic behavior; gel = Trommsdorf-Norrish effect; gl = glass effect and u
= maximum conversion

At higher conversions, one should expect a continuous decrease of the polymerization rate to zero, because
monomer concentration decreases (equation 1.15). This behavior can be realized for solution polymerization
with an adequate dissolution. In the case of higher concentrated solutions or bulk polymerization one observes an
increase of the polymerization rate at high conversions, which is named the Trommsdorf-Norrish effect.

The Trommsdorf-Norrish effect results from the increase of viscosity of the reaction medium as the reaction
proceeds. This increase in viscosity does not effect the chain propagation reaction, since the diffusion rate of the
small monomer molecules is hardly slowed down. But it results in a drastic decrease of the rate of termination.
The diffusion rate of the large macromolecular species with free radicals at the chain-end undergoing termination
is significantly decreased by viscosity of the reaction medium, which causes the loss of steady-state conditions,
and the concentration of propagating radicals to increase relatively (see equation 1.13).

This has two consequent effects on the kinetics:
Increase of the polymerization rate
Increase of the average degree of polymerization (see equations 1.16-1.19)

A dangerous consequence of the Trommsdorf-Norrish effect for processing bulk polymerization and
concentrated solution polymerization results from the reaction heat which can not be transferred in a proper way
in high viscous media. A temperature increase is a possible consequence, as well as speeding up of the whole
process, which may get out of control and lead to an explosion.

6
Therefore, bulk polymerization, in which monomer acts as solvent for their polymer, has to be carried out with
great care.

Besides solution polymerization, the Trommsdorf-Norrish effect can be controlled by suspension and emulsion
polymerization. These techniques are often used for large-scale synthesis of polymers.

1.1.5 Experimental measurement of rates of polymerization

In order to determine the rate of polymerization it is necessary to measure the monomer concentration [M] as a
function of the reaction time, as one can see from equation 1.15.

The most obvious way to do this is to weigh the amount of monomer after the reaction stopped at some
predetermined time. Alternatively, and more convenient, the amount of polymer can be weighed, since M = M
0

P. By this method absolute concentrations are obtained. (E1.1, E1.2)

In some situations, it is more convenient to measure some physical properties of the reaction mixture that are
related to [M], and change during the polymerization process. A method often used by this consideration is the
dilatometry, which is very easy to carry out.

Dilatometry

The physical property measured by dilatometry is the volume contraction of the polymerization system, which
results from the replacement of van-der-Waals bonds between monomer molecules (0.3- 0.5nm) by covalent
bonds (0.14-0.19nm) between repeating units in the polymer chains. For example, the volume contraction for a
100% conversion at 25 C is 14.14% for styrene, 26,82% for vinyl acetate, and 23,6% for MMA.

During the polymerization, the change of the liquid height in a capillary with a known diameter is measured with
time. Thus, the change of volume v with polymerization time t could be set in relation to the rate of
polymerization (equation 1.15) to obtain the rate constant k
Poly
.

The volume change with time ( ) t V is proportional to the change of conversion with time ( ) t C (in %), and
this is proportional to the rate of reaction V
R
:

t
C
v a
t
v
0
(1.21)
P
M
Poly
M t
C
V

(1.22)

where, v
0
is the volume of the monomer before the reaction starts. The proportionality constant a represents the
standardized difference of density between monomer and polymer.

M
M
P
P
M
M
M
P M
v
M
v
M
-
v
M
a

(1.23)

M
M
= molar mass of the monomer

M
P
= molar mass of the repeating unit of the polymer

v
M
= molar volume of the monomer

v
P
= molar volume of the polymer

Because M
M
= M
P
, it follows from equation 1.23:

7
P
M
V
V
- 1 a (1.24)

From equations 1.21, 1.22, 1.23 and 1.24 is obtained:

P
M
0 P M
M
P
M
Poly
M t
v

v
1

- M t
C
V

(1.25)

In this equation all terms with a density are constant and can be calculated from the molar values; v
0
is known
from the amount of used monomer, t is measured, and v is calculated from:

h
4
d
v
2
(1.26)

Section 1 Free Radical Chain Growth Polymerization Experiments
8

1.2 Experiments

E1.1 Bulk polymerization of MMA with AIBN (Trommsdorf-Norrish effect)

APPLICABILITY
This experiment is applicable to a large number of monomers polymerizable by free radical mechanisms.

SAFETY PRECAUTIONS
Dangerous chemicals are used in this experiment. AIBN is highly toxic; the monomer, dichloromethane, and
methanol are toxic, irritant, and noxious, and flammable. Adequate ventilation, including use of a fume hood, is
essential. The polymerization is highly exothermic. To afford protection in case it gets out of control, it is
necessary to shield the large glass tubes containing monomer. Safety glasses must be worn in the laboratory at all
time.

APPARATUS
basic assistant
name amount name amount
25 ml volumetric flask with stopper 1 magnetic stirrer 1
test tube with ground-glass joint NS 14 5 oil bath ( heatable, 70
o
C) 1
ground-glass stopper NS14 5 filter paper ( 70mm) 5
metal clip NS 14 5 Pasteur pipette 2
100 ml beaker 5 ice bath 1
Bchner funnel ( 70 mm) 1 water aspirator pump 1
500 ml suction flask 1 jack 1
magnetic stir bar (10-20 mm) 2 vacuum pump 1
thermometer ( 100
o
C) 1 spatula 1
rubber-gasket 1
separatory funnel (250 ml) 1 condenser NS24 1
distillation adapter NS 24 1 vacuum adapter NS 24 1
250 ml flask 1 100 ml flask 1

REAGENTS AND MATERIALS
azobisisobutyronitrile (AIBN), 200mg dichloromethane, 30ml
methyl methacrylate (MMA) (newly dist.), 20g methanol, 300ml
Anhydrous Na
2
SO
4
or MgSO
4
, 100g CuCl, 10g
NaOH (10%), 300ml N
2
gas

PREPARATION
1. Prepare methyl methacrylate in advance as follows: (students dont need to do this step)
a. Wash to remove inhibitor: The inhibitor, usually an aromatic such as hydroquinone or t-butyl
pyrocatechol, is removed by washing the monomer with 10% aqueous NaOH. Roughly equal parts of
the basic solution and the monomer are placed in a separatory funnel and mixed by tumbling. The
heavier aqueous phase is drained off. The procedure is repeated once or twice until the liquids remain
clear. The monomer is then washed with distilled water until litmus paper shows that the entire base has
been removed.
b. Dry: A drying agent such as anhydrous Na
2
SO
4
is added to the monomer (100g/l). With occasional
tumbling, drying is complete in about h.
c. Distill: Add about 1g/l CuCl stabilizer to the monomer and distill under dry N
2
at 60 torr and 33-35
o
C.
9
d. Re-distilled monomer just before use, and check before use: Test for the presence of polymer by adding
a drop of methanol. Turbidity indicates the presence of polymer.

2. Re-crystallize AIBN as required by preparing a saturated solution in methanol and cooling in a refrigerator.
Collect the crystals on a fritted-glass filter when about 60% of the solvent have evaporated.

PROCEDURE (Approximate time: 3 h)
100 mg azoisobutyronitrile (AIBN) and 10 g of newly distilled methyl-methacrylate (MMA) are added into a 25
ml volumetric flask, and shaken carefully to make AIBN dissolved. Remove oxygen by bubbling nitrogen via a
pipette through the solution, from which five portions (3 with 2 g and 2 with 1 g) are divided with a 2 ml pipette
into five test tubes with ground-glass joint. Oxygen has to be removed again. After closing the test tubes with
glass stoppers and metal clips, place in an ice bath before polymerization. Polymerization reaction is carried out
in a oil bath at 70 C (exact temperature control is important!!!). After 10, 20, and 30 minutes one of the 2 g test
tubes is removed from the water bath and cooled down in an ice/salt bath. The 1g test tubes are removed when
gas is generated. Write down the time (ca. 40- 50 min) and take out the last one 2 min. later.

Work up: Dilute each of the samples with 2-5 ml dichloromethane. By dropping each of these solutions into 50
ml of stirred methanol, the polymers are precipitated. The polymeric precipitates are filtered with suction,
washed with methanol and dried over night at 60 C in vacuum. The next day the polymers are weighed.

EVALUATION
Q1.1.1 Why should oxygen be excluded?

Q1.1.2 Make a plot of the time dependence of the conversion (P).

The conversion is calculated from:

0
t 0
[M]
[M] - [M]
P(t)
PMMa
20C
=0.944 g/ml
PMMa
70C
=0.90 g/ml
How would the graph look like without a Trommsdorf-Norrish effect?

Q1.1.3 From the slope of the graph (V
Poly
/[M]
0
), determine the rate constant of polymerization (k
Poly
) with
equation 1.15.

From k
Poly
and f = 0.5 ; k
d
= 2.75*10
7
[l/mol*s] ; k
i
= 3.7*10
-5
[1/s], calculate k
p
and compare it with the
value from the literature.

Q1.1.4 Calculate the amount of initiator, which is dissociated at the end of the reaction.

Q1.1.5 Gas is produced in sample 4 and why?

REFERENCES
Gorge W. Odian, Principle of Polymerization, 3rd Ed, John Wiley & Sons 1991.

Stanley R. Sandler Wolf Karo, Eli M. Pearce, Polymer Synthesis and Characterization : A Laboratory
Manual, Academic Press 1998.

10
E1.2 Suspension polymerization of styrene with dibenzoyl peroxide (BPO)

APPARATUS
basic assistant
500 ml three-neck flask NS 29 1 magnetic stirrer 1
glass stirrer bearing 1 silicon bath 1
glass stirrer shaft 1 filter paper 5
coil condenser 1 jack 1
contact thermometer 1 water aspirator pump 1
quick fit NS 29 1 KPG-stirrer 1
nitrogen-inlet adapter 1 100 ml beaker E1.1
100ml round-bottom flask 1 magnetic stirring bar E1.1
stopper NS 29 1 100 ml separatory funnel 1
wide glass tube (30 cm) 1 250 ml beaker 2
pipette pump 1 Buchner funnel 1
25 ml graduated cylinder 1 rubber-gasket 1
conical funnel 1 500 ml filtering flask 1

ploy(vinyl alcohol) (PVA), 2g
dichloromethane, 250ml
dibenzoyl peroxide (DBPO), 1.0g
methanol, 1500ml
styrene (newly dist.), 50g
anhydrous MgSO
4
, 300g
CuCl, 50g
NaOH (10%), 300ml

PREPARATION
Prepare styrene in advance as follows:
a. Wash to remove inhibitor: The inhibitor, usually an aromatic such as hydroquinone or t-
butylpyrocatechol, is removed by washing the monomer with 10% aqueous NaOH. Roughly equal parts
of the basic solution and the monomer are placed in a separatory funnel and mixed by tumbling. The
heavier aqueous phase is drained off. The procedure is repeated once or twice until the liquids remain
clear. The monomer is then washed with distilled water until litmus paper shows that the entire base has
been removed.
b. Dry: A drying agent such as anhydrous Na
2
SO
4
is added to the monomer (100g/l). With occasional
tumbling, drying is complete in about h.
c. Distill: Add about 1 g/l CuCl stabilizer to the monomer and distill under dry N
2
at 20 torr and 40-43
o
C.
(Note: It is not essential that the monomer be dried and distilled after step (a) if it is to be used only for
suspension polymerization. However, nitrogen should be bubbled through it to remove oxygen.
Monomer treated in this way should be stored in a refrigerator for no more than 24h before use.)

PROCEDURE (Approximate time: 8h)
Add 300 ml dist. water and 0,5g ploy (vinyl alcohol) in a 500ml three neck flask equipped with a precision glass
stirrer, a coil condenser with gas inlet, and a internal thermometer (quick fit), and warm up to 60-70C on a
silicon bath with stirring until the ploy (vinyl alcohol) is dissolved completely. Meanwhile, oxygen is removed
by bubbling nitrogen through the solution (replace the internal thermometer with a Pasteur pipette). Dissolve
0,75 g dibenzoyl peroxide (BPO) in 50 g of freshly distilled styrene in another flask at room temperature, and
pour this solution into the 500 ml flask with stirring. The stirring velocity is chosen so that the styrene can be
distributed in small droplets of about 0.1-0.5 cm diameter (about 250 rpm). This velocity has to be held constant
11
during the Polymerization process! Replace the Pasteur pipette with the internal thermometer and connect the
condenser to nitrogen, then heat the suspension up to 80-85 C.

With a countercurrent of nitrogen gas, take a 20 ml sample with a glass tube, at reaction time T = 0 (end of
Styrene addition), 30, 60, 90, 120, 150, 180, 240, 300, and 360 minutes. Pour each of the samples into 20ml
dichloromethane in a separatory funnel, shake then separate the organic layer. The polymer is precipitated with
80 ml methanol, filtered with suction, and dried at 50C over night. After 6h the polymerization mixture is
cooled down to room temperature with stirring. Then stop stirring. After a few minutes water phase is
decantated, the ploy (styrene) pearls are filtrated, washed with methanol and water, and dried at 50 C. Weigh
the samples and calculate the total yield.

Store the samples for molecular weight determination and spectroscopy measurement.

EVALUATION

Q1.2.1 Make a plot of the time dependence of the conversion (P) (see Q1.1.2)

Q1.2.2 Calculate the reaction rate (rP) (see Q1.1.3)

12
E1.3 Dilatometry (polymerization rate constant of styrene with AIBN)

APPARATUS
Basic assistant
Name amount name amount
50 ml round-bottom flask NS 14 3 thermostat 1
glass stopper 3 cardboard 1
metal clips with screw 3 graph paper 3
dilatometer 3 cellulose
15 l beaker 1 silicon grease 1
Pasteur pipette 2

styrene (newly dist.), 200 ml dichloromethane, 200 ml
dibenzoyl peroxide (DBPO), 10 g acetone, 200 ml

PROCEDURE
The dilatometer is shown below:
h

It consists of the capillary tube (1), the reaction flask (2), the inlet funnel (3), and the stopcock (4)

Put the components of the dilatometer together (capillary tube with funnel and stopcock, reaction flask)
thoroughly greasing the Stopcock and the joints. Fix the flask with a metal clip and weigh the empty apparatus.
Note down the weight of the apparatus and the diameter of the capillary, which is engraved on its top. Do the
same for all three dilatometers. Take care not to exchange any part of the apparatus after weighing. Heat up a
water bath with the thermostat to 50 C.

Make three scales out of some graph paper and a piece of cardboard for each dilatometer and fix them with
adhesive tape to the capillary tube. (The scales are needed for determination of h)

After this preparation, dissolve different amounts of the initiator in 60g of styrene in a 100 ml, nitrogen-flushed
flask by shaking carefully to prevent blistering, which would introduce into much oxygen. After completely
13
dissolving the initiator, fill as much the styrene as necessarily via the funnel to fill up the apparatus to the lower
end of the capillary tube without any bubbles. Close the stopcock and dab away all the styrene in the funnel
carefully with cellulose or paper.

Group Entry A (mg) Entry B (mg) Entry C (mg)
1 380 460 540
2 400 480 560
3 420 500 580
4 440 520 600

Now, immerse the apparatus into the water bath (50 C) up to the lower end of the capillary tube.

CAUTION: Due to the thermal expansion of the styrene, it comes out of the upper end of the capillary and has
to be removed by dabbing away with a cloth. The cloth should be disposed afterwards. The experiment is
sensitive to air movement.

After reaching the thermal equilibrium the meniscus of the liquid in the capillary starts to fall down. Now,
measure the change of the height of the meniscus in relation to time. The time interval depends on the initiator
concentration and has to be chosen usefully. The measurement is carried out until the meniscus of the liquid
reaches the lower end of the capillary tube. (If the reaction is very slow, minimum time will be 90 min.)

In order to obtain good data, it is helpful that the same person (parallax) reads them!

After the measurement remove the apparatus carefully from the water bath and wipe off the water on the outside.
Weigh the filled dilatometers. From the difference in weight of the filled to the empty dilatometer, the volume of
styrene is to be calculated by taking into account the density of styrene (
20C
= 0,9063 g/ml).

Clean the apparatus thoroughly, first by washing with dichloromethane and then acetone.

Do all three experiments parallelly (A, B, C), because you have to repeat them again. In the end you should have
six sets of data.

FUNDAMENTAL EQUATIONS
At the reaction temperature,
1 1
- 1

27
1

28
conv.% =
V
t
V
100
100
60
x
M
s
1000
V
POLY
= 1

29
-

where, V
100
represents the volume contraction at 100% conversion of styrene, W represents
the weight of monomer used, x represents the conversion speed of monomer per minute, M
s

represents the molecular weight of monomer,
m
and
p
represent the density of monomer and
polymer at the experiment temperature, respectively.

14
EVALUATION

Q1.3.1 Determine the rate of polymerization for the different initiator concentrations.

For the determination of polymerization rate the h = h
max
-h
t
has to be calculated first for every t. h
max
is
measured from the meniscus of the liquid after the thermal expansion of styrene.

The h is plotted against t. From the slope of the graph and equation 1.15, calculate the polymerization rate
(VPoly).

Q1.3.2 Why is a deviation from the straight line in early stage of polymerization observed?

The rates of polymerization for different initiator concentrations should be plotted on a double logarithmic paper
against [I]. Discuss the plots.

Section 2 Anionic Polymerization Introduction
15
Section 2 Anionic Polymerization

2.1 Introduction

Anionic polymerizations proceed via metalorganic sites: carbanions (or oxoanions) with their counterions for
electrical neutrality. They enable the synthesis of well-defined macromolecules by control of molecular weights
and molecular weight distribution, and give access to functional polymers, block copolymers, branched species,
and others. But their industrial interest is limited, because they usually require solvents which make large scale
processing is expensive.

If the polymerization system complies with certain conditions (see below) the mechanism of anionic
polymerization is quite simple. The polymerization is initiated by the nucleophilic attack of a metalorganic
compound onto a monomer (predominately vinylic monomers).

R
R M
R
R
M
(2.1)

The carbanionic site is restored at the chain end and is able to attack other monomers during the propagation.

R
R
R M
R
R R
M
(2.2)

After consumption of the monomers, the chain end stays carbanionic until the reaction is quenched by addition
of an electrophile. Propagation proceeds if a new monomer is added instead of an electrophile. Thats why this
kind of polymerization is called living, because the reactive site stays alive as long as no other electrophile is
present. (A few anionic polymerizations are not living processes see literature) Termination reactions by
mutual annihilation, a characteristic for free radical polymerization, have no counterpart in ionic polymerization.

The conditions that monomers, initiators, and solvents have to fulfill in order to obtain a living anionic
polymerization are:

Monomer
a) It should be fitted with an electron withdrawing substituent, giving rise to polarization of the double bond
and capable of stabilizing the carbanion to be formed.
b) It should not contain any acidic hydrogen atoms.
c) It should not contain any strongly electrophilic function capable of yielding side reactions with carbanions
or oxoanions.
d) The carbanion arising from the monomer should be able to attack the monomer, thus allowing the
polymerization.

Initiator
For each monomer the most appropriate initiator should be selected, which is sufficiently active to react
rapidly and quantitatively with the monomer (to initiate the polymerization) but unable to give rise to side
reactions with the electron withdrawing group of the monomer. The most highly nucleophilic initiator is not
always the best choice.

Solvent
a) It has to be aprotic to prevent transfer and side reactions.
b) It has to be free of any electrophilic function groups, which may react with the carbanionic sites.
c) It must allow the polymerization to proceed in homogeneous phase, i. e., it should dissolve the polymer.

2.1.1 Kinetics, molecular weight, and molecular weight distribution of living anionic polymerization

2.1.1.1 Kinetics

If I
-

represents the carbanionic site of the initiator, M the monomer, and M
i
-
the living chain end of a polymer
molecule with degree of polymerization i, the initiation step can be schematized as:
16

+
1
M M I (2.3)

The propagation steps can be schematized as:

+
+
i 1 - i
2 1
M M M
.
.
M M M
(2.4)

The consumption rate of the initiator is expressed by:

[M] ] [I k
dt
] I [ d
I

(2.5)

That of the monomer by:

[M] ] M [ k
dt
] M [ d
Pr

(2.6)

[M
-
] means the total concentration of living chains of all degrees of polymerization
1 i
i
] M [ .
This concentration is constant (no termination) and, if initiation is fast enough, is equal to initiator concentration
[I
-
]. Therefore the reaction rate is first order with respect to monomer concentration.

Integration of this first-order rate equation gives the time ratio to the monomer concentration.

t ] M [ k
] M [
] M [
ln
Pr
0
(2.7)

A plot of the logarithms versus t gives a straight line with slope k
Pr
[M
-
], from which the rate constant can be
calculated since [M
-
] is known.
The rates are measured experimentally in the same way as in free-radical polymerization, namely, by the
measurement of the monomer concentrations at various times or by dilatometry.

2.1.1.2 Degree of polymerization

Because no termination step exists in a true living polymerization, the degree of polymerization after complete
consumption of monomer is simply given by the mole ratio of monomer consumed to initiator introduced.

] I [
] M [ ] M [
P
0
n

(2.8)

2.1.1.3 Distribution of degree of polymerization

The most important difference between a living ionic polymerization and a free radical polymerization is that the
distributions of polymerization degree are quite different. The distribution of living ionic polymerization is the
Poisson-type whereas that of free-radical polymerization is disproportionate and polycondensation is the Flory-
Schulz type. Poisson-type distribution is obtained upon distributing randomly p objects to q boxes provided p >>
q. This is exactly the case in living anionic polymerization where p monomer molecules are distributed among q
growing chains.

Kinetic considerations lead to an expression for the weight fraction w
i
of the living species of polymerization
degree i and the mole fraction x
i
of molecules with a degree of polymerization i (for derivation see literature).

17
)! 1 i (
i
e
1
w
) 2 i (
i

(2.9)

e
)! 1 i (
x
) 1 i (
i
(2.10)

Both equations describe a Poisson distribution. Where, is the average kinetic chain length meaning the average
number of growth steps per living chain, which have taken place during the whole process. For these kinetics,
equals the average degree of polymerization minus one ( =P
n
1).

The number average molecular weight results from multiplying number average degree of polymerization by the
mass of the structural unit (m
0
).

0 0 n n
m ) 1 ( m P M + (2.11)

From the general definition of the weight average degree of polymerization

i
1 i
0 i
i
1 i
i i w
i m w M w M (2.12)

and equation 2.9, results following in a living anionic polymerization:

0 w
m
1
1 M
]
]
]
,
,
+
+ + (2.13)

Therefore the polydispersity index is given by:

2
n
w
) 1 (
1
M
M
+
+ (2.14)

From equation 2.14 it follows that polymers with high degree of polymerization should exhibit low
polydispersities, i.e., close to 1. This is special among living ionic polymerization.

2.1.2 Influence of the solvent on steroeselectivity and the rate of polymerization

The influence of solvent on the nucleophilic reactions involved in anionic growth reactions can be expected to be
high. Polymerization rates and stereoselectivities are strongly influenced by the solvation of the counterions of
growing macroions, because nearly all common polar solvents are Lewis bases and the cations are more or less
strong Lewis acids. This influence results from the degree of dissociation of the ion pair at the growing chain
ends. The degree of dissociation can be represented as follows:

R M R // M R + M
Contact
ion pair
Solvent-separeted
ion pair
Free
ions
Solvation Dissociation
(2.15)

2.1.2.1 Rate of polymerization

It is known that metal organic compounds tend to aggregate in a polar solvent to inverse micelle. The degree
of aggregation is still somewhat controversial, but it evidently influences the kinetics of polymerization process
(mainly the rate of polymerization). In the case of n-butyllithium, for instance, the aggregation degree is close to
6 and the rate of initiation in a hydrocarbon solvent is therefore 1/6th in respect to initiator concentration. It is
18
generally assumed that the unassociated contributes to initiation and chain growth. Free ions are far more
reactive than ion pairs.

The macroions aggregate as well as dissociate, Therefore, the statements made so far (concerning molecular
weight, polydispersity index etc.) remain entirely valid. This arises from the fact that the rates of aggregation and
dissociation are very high. In polar solvents the aggregation degree decreases and the equilibrium are pushed to
the free ions. That is chiefly why the overall rate of polymerization is higher in a polar than in nonpolar solvents.

2.1.2.2 Stereoselectivity

For certain monomer / initiator systems, the polarity of the solvent also has a strong influence on the tacticity of
the polymer. This is again a result of the solvation of the counterions. Considering the polymerization of methyl
methacrylate (MMA) initiated by an organolithium compound: If the polymerization is carried out in toluene,
which poorly solvates the lithium cation, the active chain ends are in the state of contact ion pairs. The only
chance for the lithium ion to receive a sufficient complexation is by the oxygen atoms of the carbonyl groups of
the polymer itself:

O
Li
MeO
O
OMe
O
Li
MeO
O
OMe
O
OMe

Because of these structures and the prochiral carbon atom of the MMA, the next attack of the carbanionic site of
the polymer chain will lead to two distereotopic transition states. One is energetically favoured and the monomer
will add mainly via this state. This leads to a stereoregularity of the polymer. This kind of stereocontrol is called
catalytic site control. The monomer is inserted between the metal center and the active chain end and the
insertion geometry is determined by the complexation of the metal center. (But catalysis is inappropriate in
chain growth polymerization, because all these kinds of polymerizations are initiated but not catalysed).

If the polymerization is carried out in a polar solvent like DME, which complexes the lithium cation very well,
then reaction takes place via free ions. The lithium is far away from the chain end and the attack of a monomer
molecule onto the chain end is not influenced by the counter ion. Nevertheless, two diastereotopic transition
states are possible, too. This time the energy is determinated only by the steric influence of the substituents at the
growing chain end, leading again to a stereoregular polymer. Therefore, this is named chain-end control.

For PMMA, one of the polymers has large syndiotactic domains and the other large isotactic ones.

2.1.3 Thermodynamic aspects / ceiling temperature

As in any other chemical reaction, polymerization is in principle an equilibrium reaction.

R
R
R M
R
R R
M
polymerization
depolymerization
(2.16)

The direction of the reaction is determined by the value of the Gibbs free energy:

S T H G (2.17)

In order to be thermodynamically feasible for a polymerization, the Gibbs free-energy change must be negative.
If it is positive, depolymerization is favoured.

The entropy change in a polymerization process is nearly always negative, because many molecules come
together to form one molecule. This results in a large loss in the number of translational and rotational degrees of
19
freedom in the system. If polymerization is predominated by de-polymerization, it must do so under conditions
where H is sufficiently negative that it compensates for the entropy loss and yields negative G.

A rise in the temperature yields a more positive entropy term, which may over-compensate the negative
polymerization enthalpy leading to de-polymerization. This is one of the main reasons for the thermal instability
of many polymers at high temperatures.

At a certain temperature the entropy term equals the enthalpy term and Gibbs free energy is zero. At this
temperature the system is at equilibrium. This temperature is the ceiling temperature (T
C
), above which no
polymer molecule can exist.

*Determination of the ceiling temperature
The relationship between Gibbs free energy and the equilibrium constant K is given by:

K ln RT G (2.18)

The equilibrium constant for a polymerization is obtained the reaction scheme

+
1 i i
R M R (2.19)

as:

[M] ] R [
] R [
K
i
1 i
+
(2.20)

With the assumption that the concentrations of the reactive chains
i
R with degree of polymerization i are nearly
equal, equation 2.20 reduces to:

] M [
1
K (2.21)

Introducing equation 2.21 and 2.17 into equation 2.18 gives:

] M [
1
ln RT S T H (2.22)

Solving this equation for ln[M] gives the temperature dependence of the monomer concentration at equilibrium:
R
S
T
1
R
H
] M ln[

(2.23)

If the monomer concentration at equilibrium is equal to the initial monomer concentration, this corresponds to
the ceiling temperature.

The ceiling temperature is obtained by measuring the monomer concentration at different temperatures, plotting
these values versus 1/T, which gives a straight line, and extrapolating to the initial monomer concentration. The
slope of straight line corresponds to the enthalpy and the abscissa intersection to the entropy.

Question: Give a list of 5 monomers suitable for anionic polymerization. Which initiator would you select for the
different monomers and why?
Section 2 Anionic Polymerization Experiments
20
2.2 Experiments

E2.1 Synthesis of Isotactic and Syndiotactic Poly (methyl methacrylate)

APPARATUS
basic assistant
25 ml Schlenk tube NS 14 4 small bowl dewar 1
septum NS 14 4 1 ml syringe with needle 3
magnetic stir bar 3 magnetic stirrer 1
250 ml beaker 2 rubber gasket 1
500 ml filtering flask 1 Buchner funnel 1
Low temp. thermometer 1

MMA (newly dist., dry), 10 ml dichloromethane, 20 ml
n-BuLi (1.6M in hexane), 2 ml dry ice/ ethanol
dimethoxyethane (DME) (dry), 20 ml methanol, 500 ml
toluene (dry), 20 ml pyridine, 2 ml

PROCEDURE
Preparation of the initiator (time: 1 h)
4 ml of a solution of n-BuLi in hexane with known molarity (1.6 M) are injected via a syringe into a well dried
nitrogen flushed Schlenk tube, which is closed with a septum. To the BuLi add 0.75 ml (1.5 equivalents) of dry
pyridine. This mixture is the initiator. Pyridine is added to avoid side and termination reactions.

Polymerization (time: 2 h)
Two polymerizations are carried out parallel (E2.1.1 and E2.1.2).

Add 15 ml of dry DME into one of the completely dried and nitrogen flushed Schlenk tubes (equipped with a
magnetic stir bar) (E2.1.1) and 15 ml of toluene into the other (E2.1.2). Close them with septa with a slight
nitrogen stream.

Inject ca. 0.5ml of the initiator to each of the tubes and cool them down to 78 C (toluene), -50 C (DME).
Under vigorous stirring add 1 ml MMA to each of the tubes. The reaction mixture should become red. If not,
there must have been some moisture in the reaction mixture. Try to add another portion 0.5 ml of the initiator.
After 20 min the tubes are replaced from cooling and the polymerizations are stopped by slowly adding 0.5
1ml methanol.

WORK UP
The polymer from E2.1.1 (DME) is precipitated by dropping the solution into 75 ml of stirred methanol,
meanwhile the polymer from E2.1.2 (toluene) is diluted with 5-10 ml of dichloromethane prior to precipitation in
150 ml methanol. The polymers are filtered with suction, washed with methanol, and dried in vacuum at 40 C.
Determine the yields and melting points of the polymers.

EVALUATION
Store the polymers for IR and
1
H-NMR analysis for the determination of their tacticity.

The table below gives the wave numbers of the IR spectra which are sensitive to the tacticity of the polymers (+
indicates the relative intensity).

21
cm
-1
677 790 808 945 1035 1100 1212 1240 1338
syndiotactic ++++ ++++ ++++ ++++ ++++ ++++ ++++ ++++ ++++
atactic +++ ++++ +++ +++ +++ +++ +++ +++ +++
isotactic 0 ++++ ++ 0 + 0 0 + ++

Q2.1.1 Compare the IR Spectra of the Polymers E2.1.1 and E2.1.2 with the spectrum of the PMMA made by
free radical polymerization (E1.1). By comparing with the IR spectrum of free radical polymerized
PMMA (atactic), make a qualitative conclusion to the structures of E2.1.1 and E2.1.2.

Q2.1.2 Explain the different tacticity of E2.1.1 and E2.1.2 with the polarity of the solvents and the structure of
the transition state.

22
E2.2 Determination of the ceiling temperature of -methyl styrene

APPARATUS
Basic assistant
Name amount comments name amount
25 ml Schlenk tube NS 14 5 E2.1 water bath 5
septum NS 14 5 E2.1 Thermometer (100
o
C) 5
magnetic stir bar 5 E2.1 500 ml beaker 2
glass stopper NS 14 5 E2.1 Bchner funnel 1
metal clip NS 14 5 E2.1 rubber gasket 1
1 ml syringe with needle 2 500 ml suction flask 1
5 ml single-use syringe 1 vacuum adapter NS 14 1

-methyl styrene (over CaH2), 30 ml methanol, 2 l
n-BuLi, 10 ml (in hexane) dichloromethane, 60 ml
acidic acid, 2 ml

PROCEDURE
Dry 5 Schlenk tubes thoroughly and close them with septa. Add ca. 5 ml of the -methyl styrene (stored over
CaH2) into each Schlenk tube. The amount of -methyl styrene is determined by weighing the empty and the
filled tubes. Start the reaction by injection of 1.5 mol % of n-BuLi into each tube and replace the septa with a
glass stopper. Then place the Schlenk tubes in the 5 thermostats at the temperatures given below. Keep them
there for about 20 h until equilibrium is reached.

Polymerization conditions
Entry 1 2 3 4 5
Temperature (C) 41 43 45 47 49
Reaction time 20 20 20 20 20
n-BuLi (mol.%) 1.5 1.5 1.5 1.5 1.5
-methyl styrene(g)
n-BuLi (mol)

Work up
Make a solution of 50 ml of dichloromethane and 0.5 ml conc. acetic acid. Inject 10 ml of this solution to each
tube. The reaction mixtures are then dropped into 400 ml of methanol each. Filter the precipitated polymers
under suction and dry them at 40 C in vacuum. Determine the yields.

Entry 1 2 3 4 5
Yield (g) polymer
Yield (%) polymer

Evaluation
Calculate the concentrations of the monomer (M
Eq
) from the polymer yields for each entry. Make a plot of lnM
Eq

against 1/T from which you should determine the ceiling temperature by extrapolation to M
0
. Determine the
enthalpy of the polymerization from the slope of the straight line and the entropy from the abscissa intersection.

Section 3 Copolymerization Introduction
23
Section 3 Copolymerization

3.1 Introduction

In the polymerization of a mixture of two or more monomers, the rates at which different monomers add to the
growing chain determine the composition and hence the properties of the resulting copolymer. The order as well
as the ratio of amounts in which monomers added are determined by their relative reactivities in the chain-
growth steps, which in turn are influenced by the nature of the end of the growing chain, depending on which
monomer added previously. Among the possibilities are random and regular alternating addition as well as block
formation.

In condensation copolymerization, the reactivities of functional groups are often independent of other
considerations and the results are trivial: Random addition occurs in the same ratio as the concentrations of
monomers in the mixture. The situations for free radical and other types of chain polymerization are similar. The
following discussion is limited to the free radical case.

With two monomers present, there are four possible propagation reactions, assuming that growth is influenced
only by the nature of the end of the growing chain and of the monomer:

M
1
+ M
1
M
1
M
1
+ M
2
M
2
M
2
+ M
1
M
1
M
2
+ M
2
M
2
k
11
k
12
k
21
k
22

With the definition of reactivity ratios r
1
= k
11
/k
12
and r
2
= k
22
/k
21
and the application of the steady-state
assumption, one can derive a copolymer equation relating the instantaneous composition of copolymer being
formed, d[M
1
]/d[M
2
], to the monomer concentrations:

d[M
1
]/d[M
2
] = [M
1
] ( r
1
[M
1
]+ [M
2
] ) / [M
2
] ( [M
1
] + r
2
[M
2
] ) (3.1)

The reactivity ratios are ratios of the rate constants for a given radical adding its own monomer to that for its
adding the other monomer. A value of r > 1 means that the radical prefers to add its own monomer, and vice
versa. In the system styrene-methyl methacrylate, r
1
= 0.52 and r
2
= 0.46, which means each radical adds the
other monomer about twice as fast as its own.

Copolymerizations are classified according to values of the product r
1
r
2
. When r
1
r
2
= 0, neither monomer radical
will add its own monomer, and propagation can only continue by adding first one, and then the other monomer
to produce an alternating copolymer. The usual case is 0 < r
1
r
2
<1, with both reactivity ratios less than 1, as in
the example given above. When r
1
r
2
= 1, the copolymerization is said to be ideal, since r
1
= 1/r
2
and each radical
shows the same preference for one of the monomers. The sequence of monomers in the copolymer is completely
random, determined only by the composition of the comonomer feed. When one reactivity ratio is greater than
unity, the copolymer contains a larger proportion of the more reactive monomer, and as the difference in
reactivity of the two monomers increases, it becomes more and more difficult to produce copolymers containing
appreciable amounts of both monomers. In those rare cases when both reactivity ratios are greater than one, there
is a tendency to produce block copolymers, but these are better to be prepared by anionic living polymer
techniques.

Polymerization involving three or more monomers is somewhat similar, but more complicated. Such cases are
important commercially. One example is the tough, rigid ABS resins, terpolymers of acrylonitrile, butadiene, and
styrene made as composite (two-phase) materials reinforced by graft copolymerization. Another is the EPDM
(ethylene-propylene-diene monomer) rubber, where the diene is added to provide sites for vulcanization. In the
coating field, as many as five or more monomers are often copolymerized to obtain the desired end-use
properties of, say, a paint film.

Section 3 Copolymerization Experiment
24
3.2 Experiments

E3.1 Copolymerization of styrene and methyl methacrylate

APPARATUS
basic assistant
50 ml Schlenk tube NS 14 3 Pipette, 10 ml 5
100 ml Schlenk flask NS 14 2 Pipette, 50 ml 1
glass stopper NS 14 3 syringe, 50 ml 1
metal clamp 2 syringe, 2 ml 2
magnetic stir bar 2 chromatographic column 1
septum 2 column adapter 1
500 ml beaker 1 rubber gasket 1
Bchner funnel 1 500 ml suction flask 1

styrene (dry), 20 ml toluene, 100 ml
MMA (dry), 20 ml 2 N HCl, 20 ml
AIBN, 2 g basic alox, 200 g
petrol ether, 500 ml nitrobenzene, 100 ml
phenyl magnesium bromide, 5 ml aluminum trichloride, 1 g
methanol, 500 ml acetone
cyclohexan dry ice / ethanol

PROCEDURE
Mix 8.00 g (76.8 mmol) of styrene and 7.68 g (76.8 mmol) of methyl methacrylate in a 50 ml Schlenk flask
under careful exclusion of moisture and nitrogen atmosphere. The flask is carefully closed and stored in the
refrigerator until use.

E3.1.1 Free radical copolymerization of styrene and MMA

Add 16 mg (0.1mmol) AIBN to a dried and nitrogen flushed 50 ml Schlenk tube. Then add 5 ml of the monomer
mixture to the tube under a small stream of nitrogen and close it quickly with a greased glass stopper. Fix the
glass stopper with a metal clamp. The mixture is polymerised at 60 C.

After 4 h, cool the flask to 0 C with ice and dilute the mixture with 25 ml of toluene. Precipitate the copolymer
from this solution by dropping it into 250 ml of petrol ether. The polymer is isolated by filtration under suction,
washing with petrol ether, and drying at 50 C in vacuum.

Yield: 10-20%

E3.1.2 Anionic copolymerization of styrene and MMA

Polymerization
Take 5 ml of the monomer mixture in a well dried and nitrogen flushed 50 ml Schlenk tube equipped with a
magnetic stirring bar. Close the tube with a septum under a small stream of nitrogen. Cool it to -50 C in a dry
ice/ethanol bath (temperature control). To this cooled mixture, 2 ml of phenyl magnesium bromide is added via a
syringe. After 9 min, add 25 ml of toluene and remove the flask from cooling bath, and quench the reaction by
dropping this solution into a stirring mixture of 200 ml methanol and 10 ml 2N HCl. Further work up is like
E3.1.1.

Yield: 10-20 %

Section 3 Copolymerization Experiment
25
E3.1.3 Cationic copolymerization of styrene and MMA

Preparation of the initiator
Equip a well dried 100 ml Schlenk flask with a column with vacuum adapter. Full in aluminium oxide to a high
of ca. 5 cm in the column. Connect the Schlenk flask to the nitrogen and let it stream out to vacuum adapter of
the column. Then add 60 ml of nitrobenzene in the column and let it drop into the flask. Finally there should be
ca. 50 ml of dry nitrobenzene in the flask. Replace the column with a glass stopper. To the nitrobenzene, add 300
mg of dry aluminium trichloride quickly and stir for complete dissolution.

Polymerization
Add 5 ml of the monomer mixture to a 100 ml completely dried Schlenk flask with a slight nitrogen stream.
Close it with a septum. To the monomer mixture, 40 ml of the initiator solution is added with a syringe. Shake
carefully until a homogenous solution is obtained. The polymerization takes place at room temperature. After 1 h
drop the reaction mixture into 200 ml of methanol. Further work up is like E3.1.1.

Yield: 40-50 %

Section 3 Copolymerization Experiments
26
E3.2 Block Copolymerization of Styrene and Methyl Methacrylate

APPARATUS
basic assistant
25 ml Schlenk tube NS 14 3 Buchner funnel 1
septum NS 14 3 rubber gasket 1
magnetic stir bar 2 500 ml filtering flask 1
500 ml beaker 2

dry styrene, 3 ml n-BuLi in hexane (1,6 M)
dry MMA, 1 ml 1 kg dry ice
dry toluene, 20 ml methanol, 500 ml
dry DME, 10 ml ethanol
1,1-diphenyl ethylene, 1 g trimethyl silychloride,

PROCEDURE
Two polymerizations are carried out: E3.2.1 Anionic block copolymerization of styrene and MMA and E3.2.2
Anionic homopolymerization of styrene (for comparison)

All operations have to be carried out under a thoroughly exclusion of moisture and air!

10 ml of dry toluene is distillated into each of two completely dried, nitrogen-flushed 25 ml Schlenk tubes with
magnetic stir bars. Close them under a small stream of nitrogen with septa. Into a third Schlenk tube 5 ml of
toluene are distilled. Dissolve 400 mg of 1,1-diphenyl ethylene in the tube with 5 ml toluene.

The two toluene filled Schlenk tubes are cooled down to 78 C in a dry ice/ethanol bath. Afterwards 1 ml of dry
styrene (0.909 g, 8.73 mmol) is transferred into one of the tubes (E3.2.1) and 2 ml of dry styrene into the other
(E3.2.2) with a syringe. Under vigorous stirring the polymerizations are initiated by injection of 5 mol % of n-
BuLi (ca. 0.3 ml) and 3-4 ml of dry DME in quick succession. (The same amount of initiator for both entries is
important). After 30 min 1.5 equivalent (referring to the amount of initiator) of a solution of 1,1-diphenyl
ethylene in toluene (ca. 1 ml) is injected to entry E3.2.1. Note down your observation.

After additional 10 min of stirring, inject 0.92 ml (0.873 g; 8.73mmol) of dry MMA to entry E3.2.1. Note down
your observations.

Both reactions are quenched after further 60 min by injection of 0.5 ml trimethyl silychloride. Each of the
polymers is isolated by precipitation in 150 ml of methanol, filtration under suction, washing with methanol, and
drying in vacuum at 40 C. Determine the yields of the polymers.

QUESTIONS
Q3.2.1 Calculate the molecular weights of the polymers from SEC-analysis and
1
H-NMR-Spectra (end-group
analysis with the TMS-group). Compare these results with the calculated degree of polymerization from
the initiator/monomer ratio.

Q3.2.2 Why it is possible to calculate the degree of polymerization from the initiator/monomer ratio?

Q3.2.3 How would you prove having a block copolymer from entry E3.2.1 instead of a mixture PS and
PMMA?
Section 4 Insert Polymerization Introduction
27
Section 4 Insertion Polymerization

4.1 Introduction

4.1.1 Coordination polymerization

Coordination polymerization is a chain-addition reaction that usually involved a propagating step in which
monomer is held in a coordinated way on the surface of a solid or liquid catalyst. There are, however, many
variations of the process and the presence of a heterogeneous system is not essential. Most prominent among the
large number of catalyst system are those first discovered in the 1950s by Ziegler, who found that mixtures of
transition-metal halides and aluminum alkyls polymerize ethylene to high molecular weight under mild
conditions of temperature and pressure. The most Ziegler catalyst systems now known are obtained by the
interaction of an organometallic compound or halide of a Group I-III metal with a halide or other derivative of a
group IV-VI transition metal. And there are several generations of Ziegler catalysis systems nowadays.

A polymerization mechanism of propylene is shown as following:

28

Natta contributed to this catalysis system that stereo-regular polymers can be obtained by this technique. In fact,
the coordination step between monomer and catalyst is the essential event in the mechanism of stereo-specific
polymerization. Coordination catalysts both supply the initiating species and provide the counterion
surroundings, which account for the regularity of addition to the growing chain. Coordination of the monomer on
the catalyst activates the growth reaction and brings the monomer into the proper steric arrangement for
stereospecific addition. An example is given below:

Numerous mechanisms have been postulated for stereoregular coordination polymerization. The chain is usually
anionic or cationic, but free-radical carriers are also possible. Among the monomers of industrial important
polymerized in this way are ethylene, propylene, 1-butene, butadiene, and isoprene.

A new type of polymerization based on Ziegler-Natta polymerization catalysis system, which also use metal
complexes as initiators, has been developed, called metallocene catalysis polymerization. In this new catalysis
system, methyl alumoxane (MAO) is used as co-catalyst and the polymerization could be homogeneous and a
polymer with better stereo regularity and narrow molecular weight distribution could be got:
29

30
4.1.2 Ring opening metathesis polymerization (ROMP)

General Information
Ring Opening Metathesis Polymerization (ROMP), a term coined by Grubbs, is a variant of the olefin
metathesis reaction. The reaction uses strained cyclic olefins to produce stereoregular and monodisperse
polymers and co-polymers.

Mechanism
The mechanism of the ROMP reaction involves an alkylidene catalyst and is identical to the mechanism of olefin
metathesis with two important modifications. First, as the reaction involves a cyclic olefin, the "new" olefin that
is generated remains attached to the catalyst as part of a growing polymer chain as is shown below with a generic
strained cyclic olefin:

Fehler! Textmarke nicht definiert.

The second difference is that the driving force for the ROMP reaction is the relief of ring strain. Therefore, the
second step shown above is essentially irreversible. Olefins such as cyclohexenes or benzene have little or no
ring strain and can not be polymerized because there is no thermodynamic preference for polymer versus
monomer. Strained cyclic olefins such as those shown below have sufficient ring strain to make this process
possible. Monomers based on norbornene derivatives are especially popular as they can be readily synthesized
from Diels-Alder reactions with cyclopentadiene. Only the unsubstituted bonds are ring-opened (it is very
difficult to metathesize or ROMP tri- and tetrasubstituted olefins).

Fehler! Textmarke nicht
definiert.

The polymers produced in the ROMP reaction typically have a very narrow range of molecular weights,
something that is very difficult to achieve by standard polymerization methods such as free radical
polymerization. The polydispersities (the weight average MW divided by the number average MW) are typically
in the range of 1.03 to 1.10. These molecular weight distributions are so narrow the polymers are said to be
monodisperse.

An important feature of this mechanism is that ROMP systems are typically living polymerization catalysts. For
example, one can polymerize 100 equivalents of norbornene and then add a second monomer after the first one is
consumed. ROMP is a superior method for making diblock and triblock co-polymers and permits one to tailor
the properties of the resulting material.

Such techniques are only possible if the ratio of chain initiation and chain propagation are perfectly balanced.
Therefore, for functionalized monomers in particular, it is not uncommon to try several different catalysts,
solvents, concentrations, temperatures etc. to achieve the best results.

31
Catalysts
The catalysts used for ROMP are the same catalysts used for olefin metathesis. However, one has to be a little
more careful when selecting a ROMP catalyst. If the catalyst is too active, it can metathesize the unstrained
olefinic bonds in the growing polymer chain (a process called "back-biting"), thereby reducing the molecular
weight and increasing the molecular weight distribution (polydispersity). For example, consider the synthesis of
polyacetylene by ROMP of cyclooctatetraene shown below. Backbiting occurs when the growing polymer chain
can orient to undergo an intramolecular metathesis and generate benzene, a thermodynamic sink. To prevent
backbiting in this or other systems you must make sure your catalyst does not react with internal olefins!

Fehler! Textmarke nicht
definiert.

When the reaction is complete, there are two methods for cleaving the polymer from the metal center:
1. Reaction with aldehyde. Many metathesis catalysts react with aldehydes in a [2 + 2] fashion just as they
do with olefins. The product is a metal oxo and an olefin (or polymer) capped with the former aldehyde
functionality. Often a large excess (100 equiv) of aldehyde is used. The cleaved polymer can then be
separated from the catalyst by precipitation with methanol.

2. Chain transfer. Reaction with several equivalents of diene is another way of cleaving the polymer chain.
The advantage of this method is that the cleavage does not deactivate the catalyst, permitting additional
aliquots of monomer to be polymerized. However, one does have to worry about broadening the MW
distribution:


Section 4 Insert Polymerization Experiment
32
4.2 Experiments

E4.1 Synthesis of high syndiotactic ploy (styrene) by homogeneous Ziegler-Natta catalysts

APPARATUS
basic assistant
500 ml three-necked flask 1 oil bath 1
250 ml four-necked flask 1 Bchner funnel 1
mechanical stirrer 1 rubber gasket 1
magnetic stir bar 2 500 ml filtering flask 1
Magnetic stirrer 1 500 ml beaker 2
dropping funnel, 50 ml 1

dry styrene, 30 ml dry toluene, 500 ml
CuSO
4
5H
2
O, 50 g trimethylaluminum, 20 g
(-C
5
H
5
) TiCl
3
, 0.5 g methanol, 800 ml

PROCEDURE (4 h)
Preparation of methylaluminoxane (MAO)
In a 500-ml flask equipped with a mechanical stirrer and an argon inlet were placed 35.5 g of CuSO
4
5H
2
O and
200 ml of toluene. Neat trimethylaluminum was added very slowly in a dropwise manner at 20
o
C. After stirring
for 24 h the mixture was filtered, and the filtrate was concentration under reduced pressure. The resulting solid
residue was dissolved in 2 mol/L toluene.

Polymerization procedure
A four-necked glass flask equipped with a mechanical stirrer was used for polymerization. 100 ml toluene, MAO
(Al unit) 7.5 10
-3
mol, (-C
5
H
5
) TiCl
3
1.25 10
-5
mol, and 0.15 mol styrene were charged to the flask in this
order under an argon atmosphere. The addition of styrene was taken as the start of the polymerization. The
polymerization was kept at 50
o
C, and stopped after 2 h by addition of acidified methanol. The resulting polymer
was washed with 500 ml of methanol several times and dried at 80
o
C in vacuum for 2 h.

Result from literature: polymer yield 7.64g, Mn 2.99 10
4
, Mw/Mn 2.01, 100% syndiotactic.

REFERENCES
1. N. Ishihara, M. Kuramoto, and M. Uoi, Macromolecules, 21, 3356-3360 (1988)
2. R. Po, N. Cardi, Prog. Polym. Sci., 21, 47-88 (1996)
Section 4 Insert Polymerization Experiment
33
E4.2 Ring opening metathesis polymerization (ROMP) of norbornene

APPARATUS
basic assistant
name amount comments name amount
25 ml Schlenk tube 1 filter paper 5
100 ml three neck flask 1 Buchner funnels 1
nitrogen inlet 1 500 ml suction flask 1
magnetic stir bar 2 250 ml beaker 2
glass stopper 3 rubber gasket 1

dry norbornene, 10 g dry chlorobenezene, 30 ml
1-hexene, 2 ml benzaldehyde, 2 g
tungsten hexachloride, 1 g toluene, 50 ml
tetramethyl tin, 2 g Methanol, 500 ml

PROCEDURE
Preparation of the catalyst
Weigh a thoroughly dried and nitrogen flushed 25ml Schlenk tube which is equipped with a magnetic stir bar
and closed with a glass stopper on a fine balance. Transfer the tube into the dry box (R 34.06) (dont use without
consultation!) and weigh there ca. 200 mg of WCl
6
into the tube, close it, and take it out. Determine the exact
weight by re-weighing on the fine balance. Inject 2 ml of dry chlorbenzene and 2 equivalents of tetramethyl tin.
Stir for a minute. This catalyst mixture is usable for a short time only!

Polymerization
Add 4.0 g (42 mmol) norbornene, 0.5 mol % 1-hexene, 15 ml dry chlorbenzene into a thoroughly dried and
nitrogen flushed 100 ml three necked flask, equipped with a magnetic stir bar, nitrogen inlet, and septum. Cool
the mixture to 0 C in an ice bath. Inject dropwise 0.1-0.2 ml of the catalyst solution. Wait ca. 30 s after each
drop. Note down your observation. After 1 h the reaction mixture is quenched by deactivating the catalyst with a
solution of 300 mg benzaldehyde in 5 ml chlorobenzene. Wait a few minutes before precipitating the polymer in
200ml of methanol. Filtrate with suction. Dissolve the polymer in a few milliliter of toluene. Isolate the insoluble
material by filtration with suction. From the filtrate isolate the soluble part of the polymer by precipitation in 200
ml of methanol. If there is still a strong smell of the monomer repeat this procedure. The insoluble and soluble
parts of the polymer are dried in vacuum at room temperature. Determine the yields of the soluble and insoluble
fractions of the polymer.

Q4.3.1 Determine the amount of cis- and trans-double bonds from the
1
H-NMR spectrum of the soluble part of
the polymer.

Q4.3.2 Why should you add a small amount of 1-olefine to the polymerization mixture?

Section 5 Polycondensation Introduction
34
Section 5 Polycondensation

5.1 Step-growth Polymerizations

Step-growth polymerizations (or step polymerization) are those in which the chain growth occurs in a slow,
stepwise manner. The monomer molecules react to form a dimer. The dimer then reacts with another monomer
to form a trimer, or with another dimer to form a tetramer. These dimers, trimers, etc. carry at their chain-ends
the same functionalities as the monomers and any of the molecules present in the reaction can react with each
other. A consequence is that at an early stage in the polymerization the monomer is consumed but the polymer is
not formed yet. In contrast to a chain-growth polymerization, the intermediates can be isolated at any time and
the polymerization can be stopped and reinitiated (after activation) at any time. The polymer is formed only at
high conversion.

HO
OH
COOH HOOC +
O
O
O
O
n
n H
2
O
+

Step-growth polymerization is not initiated (as in chain-growth polymerization) but catalyzed. Many of them
(but not all!) are equilibrium reactions and therefore reversible in principle.

In the category of step-growth polymerization fall the polycondensation and the polyaddition.

They differ in that all polycondensation involves the elimination of small molecules at each condensation step
between bi- or higher-functional monomers, whereas in polyaddition no small molecules are eliminated in the
addition steps.

Typical condensation polymerization is the formation of polyester and polyamide with elimination of water.
Besides water other small molecules may be eliminated like HCl (see E5.3), alcohol (during a
polytransesterification), ethylene (ADMET), or dimethylacetylene (alkyne metathesis).

A typical example of polyaddition polymer is the polyurethane (PUR) which is formed by addition of a hydroxyl
group containing monomers to isocyanates.

Polycondensation and polyaddition with bifunctional monomers are subdivided into AB reactions and AA/BB
reactions. AB monomers have both functionalities necessary for the polyreaction (e. g., hydroxyacids forming
polyesters). Only one type of monomer is needed. AA/BB reactions are carried out with two different types of
monomers, one of which has two functionalities A (e.g., dialcohol), and the other two functionalities B (e. g.,
dicarboxylicacid).

5.1.1 Kinetics of step-growth polymerization

Polycondensation and polyaddition share the same relationships between monomer conversion and degree of
polymerization for equilibrium reactions and kinetics. Statements that apply to polycondensation are thus also
valid for polyaddition (with few exceptions).

Since the degree of polymerization (DP) is the fundamental property of polymer the knowledge of the
dependence of the DP on the molar ratio of the monomers and the conversion is important.

35
5.1.1.1 Time Dependence of the Average Degree of Polymerization

Consider a AA/BB polycondensation, (for example, AA for a dialcohol, BB for diacid. If N
0A
and N
0B
are the
initial numbers of functional groups, and their ratio r is less than unity (excess of monomer B), then the total
number of structural units (molecules), N
su
, is given by

(
,
\
,
(
j +
+
r
r 1
N
2
1
) N (N
2
1
N
0A 0B 0A SU
(5.1)

The factor 0.5 has to be set because each monomer carries two functional groups.

The average degree of polymerization (DP) can be expressed in terms of the number of structural units N
su
and
the total number of molecules in the system (N) is:

N
N
DP
SU
(5.2)

N
su
stays the same during the reaction, but the total number of molecules is known only at the very beginning of
the polycondensation. So one has to express N in terms of the conversion (P).

P is the fraction of A group that has reacted at time t.

0A
A
N
N
P

(5.3)

Because functional groups A and B react with each other on a 1:1 basis ( N
A
= N
B
) and we have assumed an
excess of B, the fraction of B groups that has reacted at time t is:

0B
B
N
N
r P

(5.4)

The number of unreacted groups (N
un
) is given by:

( ) ( )
0B 0A UN
N rP 1 N P 1 N + (5.5)

Because r N N
0A 0B
and each molecule in the system carries two functional groups, the total number of
molecules in the system is given by:

(
,
\
,
(
j
+
2r
r - 1
P 1 N N
2
1
N
0A UN
(5.6)

Substitution of equations 5.1 and 5.6 into 5.2 leads to:

r - 1 P) - 2r(1
r 1
DP
+
+
(5.7)

This is the general Carothers equation, which describes the degree of polymerization in terms of the conversion
and the molar ratio of functional groups.

In the limit of r = 1 equation 5.7 reduces to:

P - 1
1
DP (5.8)

36
This is the case if one uses an exact stoichiometric reactant ratio in an AA/BB polycondensation or AB-
monomers where the stoichiometric ratio is given automatically.

5.1.1.2 Equilibrium constants

Considering a low molar mass esterification, the equilibrium constant (K) is given by:

[ ][ ]
[ ][ ] alkohol acid
O H ester
K
2
(5.9)

Most equilibrium constants are small, which means the reaction prefer to the side of the educts. In low molar
mass chemistry the yield of the ester can be enlarged by increasing the concentrations of acid or alcohol. This
strategy is not possible in polymer chemistry. In AB polycondensation A and B groups are united in one
monomer molecule. Therefore an excess of one group is not possible. In AA/BB polycondensation an excess of
one monomer would drastically decrease the degree of polymerization as shown in equation 5.7. It follows that
one has to get rid of the small molecules (for example, water).

Figure 5.1 shows the dependence of the polymerization degree on the amount of water.

Fig. 5.1 Dependence of polymerization degree on the amount of water

5.1.1.3 Molecular weight distribution of linear condensation polymers

Equation 5.7 is an expression for number average the degree of polymerization (DP = P
n
). The number-average
molecular weight (M
n
) is given by:

0 n n
M P M (5.10)

where M
0
represents the average molecular weight of the structural unit that makes up a repeating unit,
substitution of equation 5.10 into 5.8 gives:

P - 1
M
M
0
n
(5.11)

The preceding section has covered the average molecular weight and its dependence on reaction time
(conversion). However, it is also of interest to determine the distribution of molecular weights and the
37
dependence of this distribution on the reaction time. Here the assumption is made that the reactivity of functional
groups is independent of the molecule size.

The number of x-mers (N
x
; x = number of structural units in a special molecule) is given by:

( )
1 - x 2
0 x
P P 1 N N (5.12)

N
0
= initial number of molecules

The weight fraction (W
x
) distribution of x-mers as a function of conversion is given by:

( )
1 - x 2
x
P P - 1 x W (5.13)

For a derivation of equation 5.12 and 5.13 see literature.

These distributions are plotted for several values of conversion in Figures 5.2 and 5.3.

Fig. 1.2 Equation 5.12 Fig. 1.3 Equation 5.13

The plots show that high molecular weight material is observed only at high conversion, whereas the molecular
weight distribution is broadened.

Section 5 Polycondensation Experiment
38
5.2 Experiments

E 5.1 Synthesis of unsaturated polyester

APPARATUS
basic assistant
250 ml three-neck flask NS 29 1 magnetic stirrer 1
magnetic stir bar 1 silicon bath 1
quick fit NS 29 1 pipette 1
ground-glass joint Thermometer 1 aluminum foil 1
vacuum adapter NS 29 1 contact thermometer 1
distillation head 2x NS 29, 1x NS 14 1 gas inlet 1
Liebig condenser 1 250 ml flask 1
100 ml round-bottom flask NS 29 1 glass stopper 1

diethylene glycol hydroquinone
maleic anhydride styrene (stab.)

PROCEDURE

Polymerization
Set up a 250 ml three-neck flask with magnetic stir bar, an internal thermometer, nitrogen inlet, distillation head,
Liebig condenser, vacuum adapter, and receiver flask. Add 53.5 g (0.5 mol) diethylene glycol, 49 g maleic
anhydride, and 37 mg (0,02 %) hydroquinone into the flask. To get rid of the oxygen, bubble nitrogen through
the reaction mixture for 10 min. Heat the mixture to 80 100
o
C, then to 190 - 200 C on a silicon bath in a
slight stream of nitrogen. The start of the condensation is indicated by distillation of water. Every hour, take a
sample of ca. 1-2 g and determine the degree of polymerization by titration of the carboxylic end-groups (see
below). When the degree of polymerization reaches 5, 000 g/mol (after ca. 5-6 h), cool down the melt to 140 C.
Half of the polymer is poured on aluminum foil and the other is mixed with 25 g of styrene (inhibited) and
quickly cooled down to room temperature on a water bath. This mixture then is stored in a sealed flask in the
refrigerator for the cross-linking experiment in E7.2.

Determination of the Degree of Polymerization Titration of the End Groups
End group determination (equivalent method) allows the calculation of relative molecular mass if the
constitution of end groups and their number per molecule is known. This is realized in a polyesterification. The
sensitivity of end group determination depends strongly on the experimental method. Titration of the carboxylic
acid end groups delivers molecular weights up to ca. 40, 000.

For 1:1 molar ratio of maleic anhydride and diethylene glycol, there is an average one acid group per molecule.

The molecular weight is calculated from:

n V c
m
M
n

n = Number of end groups per polymer molecule
M
n
= Molecular weight of the polymer (g/mol)
m = titrated amount of polymer (g)
Section 5 Polycondensation Experiment
39
c = Concentration of the volumetric standard (mol/l)
V = Volume of the volumetric standard (l)

EQUIPMENT
Name amount comment Name amount comment
250 ml beaker 2 Burette 1
magnetic stir bar 2 magnetic stirrer 1

CHEMICALS
phenol phthalein acetone
0.1N NaOH volumetric standard dichloromethane

PROCEDURE
1-2 g sample of the reaction mixture (note down the exact amount) is dissolved in acetone or
dichloromethane/water. Take care completely to dissolve the polymer. Titrate this solution against an indicator
(phenol phthalein) until the pink color stays for a few seconds. Note down the volume of the volumetric standard
and calculate the degree of polymerization.

Typical equipment for polycondensation
Section 5 Polycondensation Experiments
40
E5.2 Synthesis of nylon 6,6 by melt polycondensation

APPARATUS
basic assistant
500 ml beaker 2 magnetic stirrer 2
magnetic stir bar 2 rubber gasket 1
Bchner funnel 1 500 ml suction flask 1
distillation head NS 14 1 50 ml pear-shaped flask 1
Liebig condenser NS 14 1 metal bath 1
vacuum adapter NS 14 1 Pasteur pipette
glass rod 1 pair of tweezers 1
receiver flask NS 14 1 mortar and pastel 1

pure adipic acid (mp152 C), 50 g ethanol, 600 ml
pure hexamethylene-diamine, 30 g

E5.2.1 Synthesis of AH-salt

PROCEDURE
Dissolve 36 g (0.245 mol) adipic acid with 300 ml of ethanol with swirling in a 500 ml flask. Dissolve 29 g
(0.25 mol) of pure hexamethylene diamine in a mixture of 80ml ethanol and 30 ml water with swirling in another
flask. If you do not obtain clear solutions, you have to filter them prior to further use.

The solution of the diamine is then added slowly (within 10 min) to the solution of the adipic acid while stirring
temperature rises to 40-45 C. After complete addition of the diamine, stir for another 30 min. Then let the
mixture cool down to room temperature and filter the precipitate. The AH-salt is washed two times with 40 ml
ethanol and dried in vacuum.

Yield: 90-95 %; mp = 183 C; pH of a 9.5 % aqueous solution = 7.62

E5.2.2 Polycondensation of the AH-Salt

PROCEDURE
Add the AH salt in a 50 ml pear-shaped flask. The flask should be half filled. Pound down the salt with the glass
rod. Connect the flask to the distillation apparatus and remove oxygen by flushing with nitrogen gas two or three
times. In a metal bath the flask is heated up to 220 C for 1 h and for another 3 h at 260-270 C. After cooling
down to room temperature, break the flask into pieces (consult the instructor!).

The polymer melts at 265 C.

Try to make a fibre by placing some of the crushed polymer in a Pasteur pipette, which is fixed vertically with a
clamp to the lattice in the hood. It is heated with a heat gun to the melting point. Figure out the best distance to
the pipette by carefully trying out with a thermometer. The molten polymer comes out of the lower end of the
pipette from where you can pull out a fibre with a pair of tweezers. Try to stretch the fibre and note down your
observations.

41
E5.3 Interfacial Polycondensation of Hexamethylenediamine and Sebacoyl Chloride

APPLICABILITY
This method is applicable virtually to all complementary pairs of monomers for polycondensation, and has been
used to produce polyamides, polyurethanes, polyureas, polysulfonamides, and ploy (phenyl esters) among others.
It is particularly useful for preparing polymers, which are unstable at the elevated temperatures required in bulk
polycondensation.

SAFETY PRECAUTIONS
Each of the reagents in this experiment is an irritant capable of causing skin burns. Care must be taken to avoid
skin contact with reagents or solutions. The solvents used are likewise hazardous because of toxicity or
flammability. Safety glasses must be worn in the laboratory at all times.

APPARATUS
basic assistant
250 ml beaker 2 blender 1
glass rod 1 pipette 1

hexamethylene-diamine, 5 g carbon tetrachloride, 200 ml
sebacoyl chloride, 5 ml acetone, 200 ml
NaOH, 5 g

PROCEDURE
Add a solution of 3ml (14 mmol) dist. sebacoyl chloride and 100 ml carbon tetrachloride in a 250 ml beaker.
Then carefully add a solution of 4.4g (3.8mmol) hexamethylene diamine, 0.3 g (7.6 mmol) NaOH and 50 ml of
water with a pipette, so that no mixture of the phases occurs. (You may color the aqueous solution with a drop of
phenolphthalein for distinguishing the phases.) On the interface, a polymer film is formed immediately. Pull the
polymer film out from the middle with a pair of tweezers and wrap the fiber around a glass rod. Now you can
roll up a continuous fiber of polyamide 6,10 on the glass rod.

Work up
Wash the coil thoroughly with a mixture of acetone and water (1:1), and dry it at 40 C in vacuum. Determine
the melting point (>200 C).

REPORT
1. Describe the experiment and apparatus in your own words.
2. Calculate the yield of polymer recovered.
3. Answer the following questions:
a. What purpose is served by the sodium hydroxide?
b. Why are the particular solvent mixtures used to wash the polymer?

42
E5.4 Synthesis of liquid crystalline main chain polymer by interfacial polycondensation

APPARATUS
basic Assistant
100 ml three-neck flask 1 ultra turex stirrer 1
gas inlet 1 centrifuge tube 2
mineral oil bubbler 1 dropping funnel 1

4,4-dihydroxy-biphenyle, 2 g methanol, 500 ml
tetrabutylammonium bromide, 1 g dichloromethane, 100 ml
NaOH, 5 g acetone, 300 ml
sebacoyl chloride, 3 ml

PROCEDURE
Equip a 100 ml three-neck flask with an ultraturax stirrer, a gas inlet, and a bubbler. Add 0.93 g (5 mmol) 4,4-
dihydroxy biphenyl, 1 g tetrabutylammonium bromide, 2.5 g NaOH and 50 ml of water into the flask. The
mixture is deoxygenated by bubbling nitrogen through the solution. Meanwhile a solution of sebacoyl chloride
and 50 ml of methylenchloride is made in a dropping funnel. Remove the bubbler from the flask, place the
dropping funnel there, and replace the bubbler on top of the dropping funnel. While stirring with maximum
speed the sebacic acid solution is quickly added to the reaction mixture. Stir the solution for a further 10 min.

WORK UP
After turning off the stirrer, let the white emulsion deposit for a while, then decant the liquid. The polymer is
then poured into 400 ml of methanol with stirring by a glass rod. Centrifugate to isolate the polymer (consult the
assistant). Wash the polymer first with methanol and second with acetone in the centrifuge tube. The solvents are
removed by decanting. Finally dry the polymer in vacuum.

Determine the yield
Store the polymer for examination with polarization microscope.

The stirrer has to be cleaned immediately after the experiment by washing first with dichloromethane and second
scouring powder and brush.

Section 6 Polyaddition Introduction/experiment
43
Section 6 Polyaddition

Polyurethane foams are classified as flexible, semirigid, and as open- or closed-cell. Flexible foam results from
the expension of a flexible polymer. Rigid foams are formed from crosslinkable comers. The semirigid foams
can be prepared from the same material used in the preparation of rigid foams, but have properties between the
flexible and rigid extremes. The open-cell foams, like sponges, have interconnecting cell structures; the closed-
cell foams consist of discrete gas-pockets completely surrounded by polymer. The reaction process could be
expressed as following:

R-N=C=O + R
'
-XH R-N -C-X-R
'
H O

R-N=C=O + H
2
O R-NH
2
+ CO
2

E6.1 Synthesis of Polyurethane Foams

APPARATUS
basic assistant
some containers like single use cups,
rubber glove etc.
5 glass rod 1
thermometer 2

Desmophen (hydroxyl group containing comp.) Desmodur (Isocyanate group containing comp.)
pigment

PROCEDURE
First add ca. 2- 3 g Desmophen in a container (a single use cup). This may be colored with a few drop of
pigment. Then add Desmodur quickly with stirring to a homogenous mixture (amount given below). The reaction
starts after 30 90s. Pour the mixture then into a rubber glove, where it foams. After the end of foaming, cool
down to room temperature.

ratio (wt.) Group A Group B Group C
Desmophen 1 1 1
Desmodur 1 2 3

Compare the different samples and note down your observations concerning the mechanical properties (softness,
stiffness, pore size, etc.)

Explain your observations.

Section 6 Polyaddition Introduction/experiment
44
E6.2 Synthesis of polyurethane elastomer

APPARATUS
basic assistant
Three neck flask, 1 NS 29, 2 NS 14 2 glass stirrer bearing 2
thermometer 2 Glass stirrer shaft, NS 29 2
Dropping funnel, 100 ml, NS 14 1 Mechanical stirrer 1

Polytetrahydrofuran, Mw 2000, 1 kg 1,2 - propyl diamine, 100 ml
2,4 toluene diisocyanate, 500 ml N,N - dimethyl formamide

PROCEDURE (5 h)

Preparation of prepolymer
To a 100 ml, dry, nitrogen-flushed three flask equipped with a mechanical stirrer, and thermometer is added 50 g
polytetrahydrofuran (Du Pont Co., Mw 2000, 0.025 mol), and vacuum for 30 minutes with stirring at 100 120
o
C, then cool down to room temperature, and add 8.7 g of 2,4 toluene diisocyanate with stirring. Afterwards,
increase the temperature to 85
o
C, and keep stirring at this temperature for additional 2 h, then vacuum the
reaction mixture to get out air bubbles involved in the material. Cool down to room temperature. NCO calc.
3.75%.

Chain extension
To a 100 ml dry, nitrogen-flushed three flask equipped with a mechanical stirrer, dropping funnel, and
thermometer are added 10 g of prepolymer and 10 ml DMF. Keeping at 5 8
o
C, a solution of 1, 2 propyl
diamine (032 g, 4.26 mmol) in 20 ml of DMF is addede dropwise over 30 60 minutes period. Stirring at room
temperature for an additional 1 h.

Pour this viscosity solution to 1000 ml water to precipitate the polymer, and wash the polymer with pure water
two times. Test the elastomer of the polyurethane you got by hand.

Q6.2.1 What should you take much care if you hope to get a polyurethane with high molecular weight?

Q6.2.2 Describe the structure of the polymer you got, and explain the reason for the elastomeric properties.
Section 7 Reaction of polymers Introduction
45
Section 7 Cross-linking Reaction of Polymer

E7.1 Synthesis of ion-exchange resin

APPARATUS
basic assistant
250 ml three neck flask 1 Pulver mhle
thermometer 1 sieves
coil condenser 1 large test tube 3
magnetic stir bar 1 mortar and pastel 1
Burette 1 100 ml beakers 3
quick fit 1 stopper 3

phenol, 25 g 2 N HCl
sodium hydrogen sulfate (NaHSO
4
), 10 g 0.1 M NaOH
sodium sulfate (Na
2
SO
4
), 10 g 0.1 M HCl
paraformaldehyde [(CH
2
O)
n
], 20 g phenol phthalein, several drops

PROCEDURE
Add 23.5 g (0.25 mol) of phenol, 6.5 g (62.5 mmol) sodium hydrogen sulfate, 7.9 g (62.5 mol) sodium sulfate,
18.75 g (625 mmol) of paraformaldehyde and 2.8 g of water into a 250 ml three-neck flask equipped with
magnetic stir bar, coil condenser, and internal thermometer. The mixture is heated to 60-70 C while vigorous
stirring. The temperature of the mixture rises quickly up to 120-130 C when the reaction starts. Therefore
remove the heating bath after the start of the reaction. Stir the yellow solution as long as it becomes viscous (at
ca. 110 C). Then immediately pour the mixture into large test tubes until they are half filled. Place these test
tubes into a drying cabinet at 100 C for 2 h and afterwards at 80 C over night. The colour of the polymer
should then be purple.

After cooling down to room temperature, break the test tube carefully, and crush the resin with a mortar and
pastel to particles of maximum 0.5 cm diameter. Crush it then with a bash mill (use a sieve with 0.7 lattice) to
particles smaller then 0.7 mm of diameter. Sieve this powder again with sieves of different pore diameters (0.7
0.1 mm) which are done by washing out the granulation with dist. water. The fraction from 0.7 to 0.5 mm is used
to determine the capacity of the ion exchanger.

Because the ion exchanger synthesized is in its neutral form (Na-salt), it has to be transformed to the protonated
form. For this purpose it is filled with the help of dist. water into a small column and washed with 100-250 ml 2
M HCl. Finally it is washed with dist. water until the water drained out is neutral. Let the resin air dry.

Determination of the capacity by batch process

Add 200 mg of the ion exchanger into each of three 250 ml flasks. Add 100 ml of 0.1M NaOH to each one and
then close with stoppers. During 10-12 h shake them once in a while. Take 20ml from each of the solutions and
titrate them with 0.1 M HCl against phenolphthalein. Determine the capacity of the ion exchange ability from the
average of the three measurements in mol/g.
Section 7 Reaction of polymers Experiments
46
E7.2 Synthesis of photoresist and photolytic crosslinking

APPARATUS
basic assistant
250 ml round-bottom flask 1 magnetic stirrer 1
magnetic stir bar 1 silicon bath 1
coil condenser 1 500 ml suction flask 1
3 l beaker 1 rubber gasket 1
100 ml round-bottom flask 1 Bchner funnel 1
magnetic stir bar 1 aluminum foil
petri dish 1 UV lamp 1
cardboard

pyridine, 200 ml ploy(vinyl alcohol), 5 g
cinnamoyl chloride, 6 g Michlers keton (tetramethyl diamino- benzhydrol)
acetone, 300 ml chloroform, 20 ml

E7.2.1 Synthesis of Photoresist

In a 250 ml round-bottom flask dissolve 2 g of ploy (vinyl alcohol) in 100 ml pyridine. Heat the mixture to
complete dissolution. Remove the silicon bath and quickly add 5 g of cinnamoyl chloride (mp = 35 C; melt on a
water bath prior to use). Note down your observations. Stir for another 2 h at 60 C.

After cooling to room temperature pour the solution into 300 ml of acetone and filtrate through a pre-folded filter
paper. Precipitate the polymer by adding ca. 2 l water. The polymer is filtered with suction, washed with water,
and dried in the dark at 50 C over night.

7.2.2 Photolytic crosslinking

Dissolve 1 g of the polymer in 10 ml chloroform in a flask, which is wrapped with aluminium foil to exclude
light. After complete dissolution of the polymer, add 1 ml of solution of Michlers keton (5 mg/ml). Spread out 1
ml of the polymer solution in a petri dish and evaporate the solvent at 50 C in the dark (max. 10min). Place a
stencil on the polymer surface and irradiate the dish with a UV-lamp (distance 25-30 cm) for 5 min. Remove the
stencil and wash the polymer out with several small portions of chloroform. Note down your observations.

Section 7 Reaction of polymers Experiments
47
E7.3 Synthesis of boron containing siloxane

APPARATUS
basic assistant
mortar and pastel 1 stirrer 1
250 ml beaker 1 greaseproof paper some
glass stirrer bearing 1 glass stirrer shaft 1

boronic acid, 3 g 10 % Fe(III) chloride in methanol, 3 ml
dimethyl ploy(siloxane), 50 g

PROCEDURE

Caution: The polymer can not be removed from hair and clothes easily!

1.5 g of boronic acid and 50 g dimethyl ploy (siloxane) are thoroughly mixed with pastel and mortar. The
mixture tends to get lumpy, which has to be avoided. After you have a homogeneous mixture, pour it into a 100
ml beaker and mix it with 4-5 drops of a 10 % solution of Fe (III) chloride in methanol. The beaker then is
placed into a bath at 90 C and the reaction mixture is stirred with a glass stirrer. The liquid becomes more and
more viscous. If it starts to wrap around the stirrer (after ca. 20 min), stop stirring and pour the polymer on a
piece of greaseproof paper, which then is placed into a day cabinet at 150 C for 65-70 min. You should obtain a
crumbly but not sticky mass.

Examine qualitatively the physical behavior of the polymer on slow working forces (gravity) and on shock
forces. Note down your observations.
Section 8 Polymer Characterization Introduction
48
Section 8 Polymer Characterization / General Considerations

For a routine characterisation of a low molecular weight molecule one uses NMR spectroscopy, mass
spectrometry, and elementary analysis. In most of the cases the data from these methods, if consistent, verify the
suggestion of a structure. Other methods to further prove the structure are determination of the melting point, X-
ray analysis, IR and UV/Vis spectroscopy, etc. All this methods can not be used without reservations to prove
the structure of polymer.

Mass spectrometry: This method is restricted predominately by two facts:
a) Due to the size of the polymers (molecular masses up to several million g/mol) the molecules can
not be vaporized without degradation by the usually employed techniques (EI, FAB, FD, etc.)
b) Polymers are in general polydisperse, which means that a sample of polymer consists of molecules
with different size and mass, it shows a molecular weight distribution. So, even if a polymer sample
is vaporized and the masses are detected, which one is the right one?

NMR-Spectroscopy: Due to the molecular weight distribution and the fact that every coupling nucleus in a
representative structural unit (i.e., the para-protons of ploy (styrene)) has a slightly different chemical
shift, one obtains, in general, broad signals for the nuclei. This signal can be assigned to a group of
nuclei but not to a few individual ones. Although determination of the coupling constant is an important
tool to proof the structure of a monodisperse low molecular weight compound, it is not for a polymer
because of the broad and overlapping signals, which are hardly detected. Also the relaxation times of
polymers behave differently and one has to be careful drawing conclusions from integration of the
signals. Nevertheless NMR spectroscopy is one of the most important tools to characterize a polymer.

Elementary analysis: To give a hint to the structure of a small molecule, the deviation of the measured data
from the calculated ones should not be bigger than 0.5 %. For a polymer this is hardly reached and a
deviation of 1 % or more is not an exception.

Melting point: With regard to the melting point, a polymer behaves similarly to soiled low molecular weight
compound in that there is no sharp melting point but a temperature range. This is, like others, again
caused by the molecular weight distribution of polymers. Instead of the melting point, polymer is most
often characterized by its glass temperature, which is unknown for low molecular weight compounds.

X-ray-Analysis: Again, because of the molecular weight distribution and the size of polymers, there are only a
few examples of polymer, which crystallize in single crystals. Therefore, X-ray analysis of partially
crystallized polymers gives good hints to the structure but is seldom a real proof.

Section 8 Polymer Characterization Spectroscopy
49
8.1 Spectroscopy

Spectroscopy is the measurement of changes of the energy states of molecule by interaction with electromagnetic
radiation.

The internal energy of a molecule is distributed in different discrete energy levels, which are separated from each
other by different amounts of energy. The energy levels belong to e.g. rotation, vibration, electron transitions
etc., The differences in energy, e.g., rotation levels, are of the same order and therefore a special part of the
spectrum of electromagnetic radiation may excite them. Another part of the spectrum may lead to vibration
transitions, etc.

Radio TV Micro
waves
Millimeter
waves
IR Near IR Vis UV Vacuum
UV
X-rays -rays
mm 300 3 1 0.5
nm 50000 770 390 200 1.0 0.05
GHz 1 100 600 6000
cm
-1
0.03 3.3 20 200 13000 26000
eV 6 1200
<NMR >< ESR>
< rotation > < Raman > <photo electrons>
< vibration >

< electron transitions >

To observe an interaction between radiation and molecule the resonance condition has to be fulfilled:

E2
E1
E
E=h

The energy of the radiation must equal the difference in energy of the states E1 and E2. One can detect the
absorption (E1<E2) of the radiation or the emission of radiation when an excited molecule relaxes to its ground
state (E2<E1). From the measuring of absorption and/or emission of radiation one obtains information of the
energy levels from which one can make a conclusion about the structure of the molecule or atom.

NMR Spectroscopy
Most nuclei of atoms have a nuclear spin
+
2
h
) 1 I ( I P (I= spin quantum number=1/2,1, 1 ...). This can be
imagined as a rotation of the nucleus. Since they are charged, they also have a magnetic momentum P .

Without an outer force, the spin of the magnetic moments, therefore, are randomly distributed.

If the nuclei are placed in an outer magnetic field (B
0
), the magnetic momentum orientates relative to the
magnetic field. Due to quantum mechanical considerations this can only be done in discrete levels relative z-axis
of the outer magnetic field, depending on the nuclear spin. This results in the z-component of the nuclear spin
and the magnetic momentum.

Section 8 Polymer Characterization Spectroscopy
50
z z z
P
2
h
m P

Where m represents the magnetic quantum number ranging in discrete steps from m =I, I-1,..., -I.
B
0
m=1/2
m=-1/2
m=1
m=0
m=-1
P
z
P
z
P
z
P
z
P
z

Figure 8.1 Orientation of the nuclear spins in an outer magnetic field for a
nucleus with I=1/2 like
1
H,
13
C (left) and I=1 like
2
H (right).

The different relative orientations of the nuclear spins and therefore magnetic momentum lead to different
energy levels of the orientations. The separation depends on the strength of the magnetic field. The stronger the
field the larger the separation of the energy levels (E=
z
B
0
).

B
0
m+1/2
m-1/2
0
E

Figure 8.2 Influence of the magnetic field B
0
on the separation of the energy levels
for a nucleus with I =1/2.

Irradiation with electromagnetic waves fulfilling the resonance condition leads to a transition between these two
levels. Transition proceeds as long as the two levels are equally populated. Then there is equilibrium between
excitation (absorption) and relaxation to the ground state (emission). After saturation of the upper state
irradiation is stopped and the emission from relaxation to the ground state is measured in NMR-spectroscopy.

The intensity of the signal depends on the difference in population of the energy levels in the ground state. This
difference is very small which can be shown by the Boltzmann distribution (see literature). For a magnetic field
of 7.05 tesla corresponding to a measuring frequency of 300 MHz for a proton NMR, the population of the upper
level is 0.99995 times that of the lower level. The difference in population of the energy levels can be increased
by stronger magnetic fields.

The statements made so far are used in medicine for nuclear spin topography. A body is placed in a strong
magnetic field, whereas the nuclear spins are orientated. Irradiation then leads to the spin flip of the protons of
(predominately) water.
Section 8 Polymer Characterization Viscosimetry
51
8.2 Viscometry

Linear and little branched polymers markedly increase the viscosity of a solution relative to that of the pure
solvent. This property, which is not found for low molecular weight molecules, can be used for technical
applications as well as for molecular weight and size determination. Viscometry of dilute polymer solutions
allows one to determine specific volumes of the macromolecules that are directly related to the shape and
dimension of the dissolved molecule and indirectly to molar masses. The later was first realised by Staudinger.

Measurement of Viscosity

According to Newton law of viscous flow, the frictional fore (F) that resists the flow of any two adjacent layers
is given by

F
x
z

dz
dU
A F
x
(8.1)

where A is the area of contact of the layers, dUx/dz the velocity gradient between them, and the viscosity.
When the upper plate is moved along the x-axis, the energy which is transferred from one layer to the adjacent
layer per time unit, is given by

2
2
x
Vq
dz
dU
V
dt
x
F
(
(
,
\
,
,
(
j

(8.2)

which leads, after transformation Trommsdorf-Norrish to

2
q
1
V
1
dt
x
F

(8.3)

Because F x is energy, this leads to the answer of the upper question: Viscosity is the energy that is distributed
per volume unit and time unit and the square of the velocity gradient. In other words viscosity can be increased
by reducing the volume or the velocity gradient or by increasing the amount of energy that is distributed. The
increase of the energy distribution is roll played by the polymer molecules.

The shape of a dissolved polymer molecule is not like a rod, as Staudinger assumed from the all trans-
conformation of a sketch of polymer, but more or less a dense coil. This is shown by the picture above, which
results from a molecular dynamics simulation starting from the all trans conformation of poly (ethylene)
molecules (50 and 120 C-atoms).
Due to its anisotropic bean like shape it behaves like a magnetic stir bar in solution and increases the energy
distribution and hence the viscosity.

52
F
x
z
F
x
z

The effect on the energy distribution capability of an isotropic, bowl shape object is comparable to a bowl
shaped magnetic stir bar for stirring a solution.

An expression for the viscosity of a solution of bowl shaped particles was first established by Einstein. His law
of the viscosity of bowl shaped colloids is

(
(
,
\
,
,
(
j
+
1 c
1
5 . 2
0
(8.4)

Where 0 is the viscosity of the solvent, c ([g/ml]) the concentration of the colloid and its density.
of a bowl is given by

3 3
B
r
m
. const
r 4
m 3
(8.5)

where m is the mass and r the radius of the bowl. Since c has the unit of g/ml, the viscosity is only dependent on
the mass of all particles in the solution, but not on the mass of an individual particle, which means that for an
bowl shaped polymer, like the branched polysaccharide glycogen, the viscosity is independent of the molecular
weight.

This is different for polymer coils of non-branched polymers. If one writes a similar expression for the density of
a polymer coil like

3
C
c
r
M
. const (8.6)

where M is the average mass of the polymer, one has to find an expression for the radius of the coil. This can be
derived from a random flight statistic (see literature) and leads to the Kuhns square root law:

M . const r
C
(8.7)

Substitution of this equation to the coil density Equation 8.6 leads to:

M
1
. const
C
(9.8)

This means that the coil density decreases with increase of the molecular weight. Substitution of this coil density
into the Einstein law and unifying all constant factors in Equation 8.4 gives:

(
,
\
,
(
j
+ 1 M Kc
0
(8.9)

This equation shows that the viscosity of a solution of a linear polymer depends on the average molecular weight
of the polymer and therefore it should be possible to determine the molecular weight from the viscosity of a
polymer solution.

To do so, it is not necessary to measure absolute viscosity of the solution but the relative viscosity (see Equation
9.10.

53
1 M Kc
0
+
(8.10)

Subtraction of 1 leads to the specific viscosity

M Kc 1
0
sp

(8.11)

The specific viscosity still depends on the concentration, which is why it is divided by the concentration leading
to the reduced viscosity

M K
c
sp
(8.12)

Finally, to obtain a comparable value for different polymer samples the intrinsic viscosity is defined (also
known as Staudinger index) as the limit of the reduced viscosity as the concentration approaches zero.

[ ] [ ] M K
c
lim
sp
0 c

(
(
,
\
,
,
(
j

(8.13)

The last equation is known as the Mark-Houwink equation.

You may find different names for this equation in literature. This is because it can be generalized to a scaling
law

[ ]
a
M K (9.14)

where the exponent a is dependant on the shape of the particles and can be derived similarly as shown for the
coil for different shapes. K can hardy calculate for a specific polymer, solvent, and temperature system, but it has
something to do with the stiffness of the polymer backbone. With a = 0 it becomes the Einstein equation, with a
= 1 the Staudinger equation, etc.

The Mark-Houwink equation is valid under certain conditions only:
a) for dilute solutions. Because the polymer coils aggregate at higher concentrations and imply a higher
degree of polymerization. Or general, it is valid, if the model of individual, ideal statistical coils holds
true.
b) the system (solvent, polymer, temperature) is in its theta state, which means, as mentioned, the polymer
coils behave like ideal statistical coils (a = 0.5).
Consider a low temperature and/or a bad solvent resulting in a poor solvate of the polymer. This would
lead to a more dens (bowl like) coil and a becomes some between 0 and 0.5. On the other side high
temperature and/or or a good solvent would increase the solvate and hence the polymer molecule
becomes more stretched (rod like) which results in a value of a between 0.5 and 1.
c) the measured liquid should have Newtonian behavior, meaning the velocity gradient is constant.

Section 8 Polymer Characterization Experiment
54
E8.1 Characterization of the Copolymers from E3.1.1 to 3.1.3 by IR, NMR and GPC

APPARATUS
basic assistant
tube 6 Stirrer bar 6
Magnetic stirrer 1

acetone, 50 ml methanol, 50 ml
acetonitrile, 50 ml cyclohexane, 50 ml
toluene, 50 ml

PROCEDURE

Dissolve 50 mg from each of the polymers (test tube) under mild heating in 5 ml of:

1. Acetone/methanol (2:1) (good solvent for PMMA)
2. Acetonitrile (good solvent for PMMA)
3. Cyclohexane/toluene (4:1) (good solvent for PS)

For comparison, do the same with polystyrene (from E1.2) and PMMA (from E1.1).

Note down your observations and draw conclusions concerning the structure of the polymers (E3.1.1, E3.1.2,
E3.1.3).

Check your conclusions by the interpretation of the IR- and/or
1
H-NMR-spectra of the polymers.

Explain the result by comparison of the mechanisms of the polymerizations and the electronic structure of the
monomers!

55
E8.2 Dilute solution viscosity

APPLICABILITY
The dilute solution viscosity measurement is applicable to all polymers, which dissolve to give solutions at a
temperature between ambient and about 150
o
C. Special techniques, beyond the scope of this experiment, are
required in the measurement and data treatment for polyelectrolytes or for polymers of sufficiently high
molecular weight that their solution viscosity depends upon the rate of shear in the viscometer.

SAFETY CONSIDERATIONS
Care must be taken in the use of organic solvents such as chloroform and toluene, both of which are highly
toxic; toluene is also flammable. Use these and other solvents only in small quantities in well ventilated
areas. Avoid the use of flames or sources of electric sparks. Safety glasses must be worn in the laboratory at
all times.

APPARATUS
1. Constant temperature bath, capable of maintaining 0.01
o
C at 25.0
o
C.
2. Viscometers with efflux times greater than 100 sec for the solvent (Ubbelohde viscometer).
3. Timer, graduated I 0.1 sec or less.
4. 25 ml volumetric flasks, stoppered.
5. Pipettes as required.
6. Source of filtered dry nitrogen at low pressure.
7. Fine fritted glass or 1.0m Millipore filter in suitable holder.

REGENTS AND MATERIALS

1. Poly (methyl methacrylate) or polystyrene samples prepared in former experiments.
2. Chloroform or toluene, reagent grades.

PREPARATION

Prepare ahead of time solutions of PMMA in chloroform at a concentration of 0.5 g/dl or of polystyrene in
toluene at a concentration of 1.0 g/dl. Use 25 ml volumetric flasks to make the solution: After filling the flask
with toluene, stopper and agitate gently; do not shake, as particles of polymer may adhere to the walls above
the liquid level and fail to dissolve. Repeat agitation from time to time until polymer is completely dissolved.
Allow at least 24 hours.

PROCEDURES

1. Rinse the viscometer with solvent and let it drain. Then place the viscometer in the constant-temperature
bath, securely fastened and with the upright tubes exactly vertical. Check the bath is regulating properly
at the desired temperature.
2. With a pipette or syringe, transfer exactly 10.0 ml filter solvent to the viscometer.
3. After temperature equilibrating has been achieved (a minimum of 10 min), bring the liquid level in the
viscometer above the upper graduation mark of bulb C as follows: Close tube 3 with one finger, and
apply a low pressure of filtered nitrogen to tube 1. When the desired liquid level (in bulb D) is reached,
open both tube 1 and 3. Bulb A will now drain, establishing the suspended level at the bottom of the
capillary. Allow the liquid to drain down the capillary. Start the timer exactly as the meniscus passes the
upper graduation mark, and stop it exactly as the meniscus passes the lower mark.
4. Determine the efflux time at least three times. The readings should agree within 0.1 sec or 0.1% of their
mean, which ever is larger. If they do not, repeat and apply the above test until three satisfactory
readings or a total of six readings are obtained. Accept the mean of three readings agreeing as indicated
above; if they cannot be obtained, it is likely that the variation results from foreign material in the
capillary or inadequate temperature control. Locate and remedy before proceedings.
5. Add exactly 5.0 ml filtered polymer solution to bulb B through tube 1. Mix the solution well by closing
tube B and applying nitrogen pressure alternately through tubes 1 and 3.
6. Repeat steps 2 - 4. Add another aliquot of solution as in step 5, and repeat until at least five solutions
have been measured.
7. Remove the viscometer from the bath, empty it, and rise all parts of it (including capillary and bulbs C
and D) with filtered solvent. Drain the viscometer and blow it dry with the stream of filtered nitrogen.

FUNDAMENTAL EQUATIONS

56
r
= t/t
o
(8.15)
sp
= (t -t
o
)/t
o
(8.16)
inh
= (ln
r
)/C (8.17)
sp
/C = [] + k
[]
2
C (8.18)
(ln
r
)/C = [] + k
[]
2
C (8.19)

CALCULATIONS

1. Calculate
r
by Eq. 8.15,
sp
by Eq. 8-16, and
inh
by Eq. 8.17.
2. Plot on the same piece of graph paper,
sp
/C versus C and
inh
versus C. Read [] as the common
intercept at C = 0 of the best straight lines through the two sets of points.
3. Calculate the Huggins constant k
from Eq. 8.18 and the Kraemer constant k
from Eq. 8.19. As an

additional check on the accuracy of your work, check to see that k- k
0.5.

REPORT

1. Describe the apparatus and experiment in your own words.
2. Include a table of values of C,
r
,
sp
,
sp
/C, and
inh
, and the graph prepared. Report [], k, k
the
solvent, and the temperature of measurement.

COMMENTS

Several variations are possible in the schedule of concentrations to be measured in this experiment. For
example, instead of adding five aliquots of 5 ml each to 10 ml solvent, the following schedules are suggested:

a. Add 10 ml stock solution to 10 ml solvent, then successively dilute with further additions of solvent.
b. Start with stock solution, and successively dilute with solvent. Determine the efflux time of the solvent
separately.

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Basic Laboratory Course

from Eq. 8.18 and the Kraemer constant k

from Eq. 8.19. As an

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