2014

Experiment 1: Preparation of a Polyamide by Condensation

Polymerization

Component: Polymer Chemistry

Objective:
To study and understand the formation of a polyamide (Nylon) through condensation
polymerization between surfaces technique and subsequently observe the effect of external
factors on molecular weight and polymer field.

Introduction:
Polymers are macromolecules built up by the linking together of large numbers of much
smaller molecules. The small molecules that combine with each other to form polymer
molecules are called monomers and the reactions by which they combine are called
polymerisation reactions. There may be hundreds, thousands, tens of thousands or more
monomer molecules linked together in a polymer molecule.
The two main types of polymerisation are chain and step polymerisation. In chain
polymerisation, only the monomer can attach to the growing chain. In step polymerisation, the
chain can grow by addition of monomers, oligomers and other polymer chains which involves
the reaction of bifunctional monomers. Polyamides (nylons) are polymers where the monomer
units are connected together by amide groups (-C(=O)-NH- ). They are formed by step growth
polymerisation which occurs when monomers bond together through condensation reactions
forming a polymer but leaving behind a small molecule, often water.
In order for a condensation polymerisation to continue its reaction, small molecules need
to be removed either by heating or through vacuum. However, heating would cause degradation
and this would result in the formation of polymer with low molecular weight. To avoid
degradation, polymerisation should be carried out at low temperature either by using the method
of polymerisation in solvent or polymerisation between two surfaces of solution. Condensation
polymerisation between surfaces of two solutions can produce polymers with high molecular
weight in a short period of time and easily. This type of polymerisation could be carried out at
room temperature and the types of polymers that could be formed using this technique are
polyurethane, polyamide and polyurea. Therefore, the formation of nylon 6,10 in this experiment
is through the method of reaction between two surfaces of solvents.
Nylon-6,10 is made from two monomers, one contains six carbon atoms, the other 10.
The 10-carbon monomer is sebacoyl chloride (CIOC(CH 2)8COCI), an acid chloride with a
COCI group at each end. The other monomer is a six-carbon chain with an amine group, -NH 2 at
each end. This is 1,6-diaminohexane (H2N(CH2)6NH2, also known as hexamethylenediamine).
When these two compounds polymerise, the amine and acid groups combine, each time with the
loss of a molecule of hydrogen chloride.

n H2N(CH2)6NH2 + n CIOC(CH2)8COCI

[-HN(CH2)6NH- OC(CH2)8CO-]n + 2n HCI

hexamethylenediamine sebacoyl chloride

Nylon 6,10

The word nylon is used to represent synthetic polyamides. Nylons from diamines and
dicarboxylic acids are designated by two numbers, the first representing the diamine and the
second the dicarboxylic acid. In order to produce a long chain of polymer and to expedite the rate
of kinetic reaction, the polymerisation system should be stirred vigorously to make sure that a
new surface of polymer is always produced in the system. This would ensure that polymers
produced would give a high percentage of yields. Both hexamethylenediamine and sebacoyl
chloride are not solvents in the polymerisation process between two surfaces of solutions.
Nylons are semi-crystalline polymers. The amide group -(-CO-NH-)- provides hydrogen
bonding between polyamide chains, giving nylon high strength at elevated temperatures,
toughness at low temperatures combined with its other properties, such as stiffness, wear and
abrasion resistance, low friction coefficient and good chemical resistance. These properties have
made nylons the strongest of all synthetic fibers in common use. In the stirring technique, the
non-equilibrium system that occurs eliminates the weakness that might occur in
polycondensation processes, such as
a) The necessity of high temperature
b) Longer time of reaction
c) Accurate stoichiometric balance of equivalent
Physical properties of Nylon 6,10
i.
ii.
iii.
iv.
v.
vi.
vii.

Bright yellow in colour

Less transparent
Melting temperature of 220C
Moderate crystallinity
High impact strength
Toughness
Flexibility and abrasion resistance

Uses of Nylon 6,10

i.
ii.

Used as monofilm in sports equipment.

Nylon 6,10 does not take up water as well as Nylon 6,6. This is because Nylon 6,10 has
more -CH2- in its polymer chain.

Apparatus: beaker (100ml), graduated cylinder (10ml), glass rod, thin stick, oven

Materials: H2N(CH2)6NH2, CIOC(CH2)8COCI, sodium laurel sulphate (soap powder), water,

hexane

Procedure
1. 3ml of sebacoyl chloride solution with 100mL hexane (solution A) was added into a
100ml beaker.
2. 0.01g of SLS and 2 drop of phenolphthalein were added into 3ml of 0
hexamethylenediamine with 50mL distilled water in a 250 mL beaker(solution B).
3. Solution A was added carefully into solution B.
4. A layer of polymer was formed between them. The strand of polymer (nylon) was
wrapped around the glass rod and the nylon strand was winded onto the rod with a steady
pace.
5. The polymer that formed was rinsed with water and was dried in the oven.
6. The weight of the polymer was measured.
7. The above steps were repeated using the technique as follows:
Set 1 and 2 are repeated
8. Solution A is added dropwise into B followed by step 4-6 as stated.(Set 2)

Result:
Table 1: Weight of polymer (nylon-6,10) produced
Before dried
Empty watch glass
Watch glass + polymer (nylon-

Set 1
35.8649
36.6318

Set 2
35.02017
35.9124

6,10)
Polymer (nylon-6,10)

0.7669

0.89223

After dried
Empty watch glass
Watch glass + polymer (nylon-

Set 1
35.8649
36.2935

Set 2
35.02017
35.4414

6,10)
Polymer (nylon-6,10)

0.4245

0.42123

Treatement of Data:
Characterization and Comparison of the polymers obtained.
Properties of polymers
obtained.

Part 1

Part 2

Mass
Elasticity
Stiffness (malleability)
Ability to stick to the

Lighter
Non Elastic
Non Malleable
Non sticky

Heavier
Non elastic
Non Malleable
Non sticky

surface of the watch glass

Given:
Density and molecular weight of sebacoyl chloride is 1.12 g/cm3and 239.14 g/mol.
Density and molecular weight of hexamethylenediamine is 0.84 g/cm 3and 116.21g/mol.

Mass of sebacoyl chloride = 1.12 g/cm3

3 cm3 = 3.36 g

Mass of hexamethylenediamine = 0.84 g/cm3

60%

Number of mole of sebacoyl chloride =

3 cm3 = 1.512 g

= 0.014 mol

Number of mole of hexamethylenediamine =

= 0.013 mol

The limiting agent is hexamethylenediamine.

Molecular weight of repeat unit for nylon 6,10 is 282.43 g/mol.

Theoretical yield of Nylon 6, 10 = 0.013 mol

282.43 g/mol = 3.6716 g

Part 1

Part 2

Actual yield of Nylon 6, 10 = 0.4329 g

Actual yield of Nylon 6, 10 = 0.7985 g

Percentage yield =

Percentage yield =

= 11.56%

100%

100%

= 11.47%

Discussion
As for this experiment, one can take advantage of the fast kinetics of the polymerisation
of diamines and diacid chlorides at the interface between two immiscible phases which is known

as the interfacial polymerisation. It is the reaction of monomers to form a very large molecule at
the contact between two immiscible liquid layers. The monomers are dissolved in different layers
and only come into contact at the interface.
Interfacial polymerisation can be of two types. In one case, there are two separate
macroscopic layers in contact with each other. This is called unstirred interfacial polymerisation.
Unstirred interfacial polymerisation is used to produce membranes and to create polymer by
continuous removal in a single rope. The other case is where one phase is dispersed as tiny
droplets in the other (continuous) phase by using high speed stirring. This is called stirred
interfacial polymerisation.
In this experiment, nylon is made through the reaction of diamine and a diacid chloride
instead of a diacid. This is because acid chlorides are much more reactive than acids. The
reaction is done in a two-phase system. The amine is dissolved in water and the diacid chloride
in an organic solvent. Meanwhile, phenolphthalein can be added to the lower (aqueous) phase to
enhance the visibility of the liquid interface whereas sodium laurel sulphate surfactant can
increase the rate of polymerisation. Besides that, phenolphthalein also helps to monitor the
polymerization. Pink color is due to presence of amine which is basic and it turns colorless when
reaction produce hydrogen ion which acidic. After that, the two solutions are placed in the same
beaker. The two solutions are immiscible, so there will be two phases in the beaker. At the
interface of the two phases, the diacid chloride and diamine can meet each other and will
polymerise there.
Interfacial polymerisation occurs instantly forming a thin film of solid nylon 6,10 at the
interface between two immiscible liquids. The film at the interface stops further reaction by
preventing the monomers from meeting each other (actually some monomers do reach other by
diffusion through the film but this is so slow that the film appears to have stopped growing).
Once the nylon that has already formed is removed, new nylon will continue to form at the liquid
interface. The layers will meet again and more nylon will form.
However, interfacial polycondensation is limited by the concentration of the reagents
used. Besides that, the solvent also determine the rate of polymerization. Since only the
molecules that is near to the interface will polymerize, when the concentration of the reagents
start to decrease until a certain limit, the reagents molecules in the interface of the solvents will
also dropped, thus caused the process of polymerization to halt and no more polymers will be
produced. This allows the formation of higher molecular weight polymer but with lower yield,
due to the incomplete of the polymerization process.
Nylon 6,10 is very strong due to the intermolecular forces. The most important
intermolecular force in making nylon strong is hydrogen bonding. In hydrogen bonding, a
hydrogen atom is covalently bound to an electronegative atom, such as nitrogen, oxygen or
fluorine. In nylon 6,10, the nitrogen-bonded hydrogen of one nylon chain will hydrogen bond
very strongly with the carbonyl oxygen atom of another nylon chain. These hydrogen bonds hold
the nylon chains together very tightly causing the nylon to be very crystalline. This makes the
nylon fibers very strong.

Figure 1.0

Set 1

Set 2
Figure 2.0

Set 1

Set 2
Figure 3.0

Set 1

Set 2

Figure 3.0 ,After dried and tear off to see the texture and the strand

Based on the results, both of the polymers are inelastic, brittle and low in malleability, as
it is not produced the same way as industrial nylon. But Set 1 has better malleabitliy than Set 2,
as the former able to form longer single continuous strand. A constant stirring helps the layer of
the polymer to stick evenly on the glass rod as seen in Figure 2.0. Brittle and inelastic properties
is due to low molecular weight of the polymerization.
Moreover, the polymer formed will not stick to the watch glass after drying in oven. This
because the polymer is in higher molecular weight, in which the solvent is not easy to adsorbed
on the polymer. Higher molecular weight of polymer such as polymer produced is more
hydrophobic and thus is non-stick to the surface of watch glass.

Precaution steps
1. Prepare all the chemicals in a fume hood and use gloves as the monomers are toxic and
corrosive.
2. Hexamethylenediamine and sebacoyl chloride are irritating to the skin, eyes and
respiratory system.
3. The rope of polymer film should be handled with rubber gloves, tongs and forceps until it
has been washed free of solvent and reactants.
4. Any unused polymerisation mixture should not be poured into the sink but should be
stirred until no further polymer is formed.

Conclusion
The formation of a polyamide, Nylon 6,10 can be achieved through condensation polymerisation
between hexamethylenediamine and sebacoyl chloride with the loss of a molecule of hydrogen
chloride each time.

Questions
1. Write the equation involved in the above synthesis, its chemical name and industrial
name.

Chemical name: Poly(hexamethylene sebacamide)

Industrial name: Nylon 6,10

2. Write the equations involved in the synthesis of Nylon-11 and Nylon 6,6. Synthesis of
nylon-11

Synthesis of nylon 6,6

Reference

Chapter
Three:
First
Part.
[ONLINE]
Available
at:http://dwb4.unl.edu/Chem/CHEM869E/CHEM869ELinks/www.umr.edu/7Ewlf/CHEM381/ch
ap31.html. [Accessed 31 May 2014].
Condensation polymer - Wikipedia, the free encyclopedia. [ONLINE]
at: http://en.wikipedia.org/wiki/Condensation_polymer. [Accessed 1st June 2014].

Available

One Part of Chemistry: Nylon 6,10 Nylon 6,6 and Nylon 11 Synthesis. [ONLINE] Available
at: http://1chemistry.blogspot.com/2013/05/nylon-610-nylon-66-and-nylon-11.html?
utm_source=BP_recent. [Accessed 1st June 2014].
Polymers:
Demonstration
3.
[ONLINE]
at: http://matse1.matse.illinois.edu/polymers/c.html. [Accessed 2nd June 2014].

Available