CHEM-E2145 Polymer Reaction Engineering

February 07, 2017

Condensation polymerization
Contents
1. Introduction ........................................................................................................................... 3
2. Solutions for the given tasks ................................................................................................. 3
2.1. Task (a): Reaction equation for the given polymerization ................................................ 3
2.2. Task (b): Number-average degree of polymerization and extent of reaction .................... 3
2.3. Task (c): Reaction carried out in a closed system ............................................................. 4
2.4. Task (d): Reaction carried out with removal of water ....................................................... 6
2.5. Task (e): Number-average molecular weight .................................................................... 6
3. Remarks ................................................................................................................................. 7
References .................................................................................................................................... 7

Attachment 1: Excel file

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1. Introduction

In this homework condensation polymerization was studied for an equimolar reaction between
adipic acid and hexamethylene diamine. This particular polymerization is well known in the
[1]
production of an industrial polyamide, Nylon 6,6 . The solutions for the tasks given are
presented in this report.

2. Solutions for the given tasks

2.1. Task (a): Reaction equation for the given polymerization

The polymerization reaction takes place according to the reaction Scheme I below. [1]

Scheme I [1]

2.2. Task (b): Number-average degree of polymerization and extent of reaction

This task required calculation of the number-average degree of polymerization as a function of
extent of reaction and drawing the curve. In this particular case, the relationship between these
two parameters is described by Equation (1), where is the number-average degree of
polymerization and is the extent of reaction (in fraction) [2].

1
= (1)
(1 )

Here, was not given, In order to explore the behavior of number-average degree of
polymerization as function of extent of reaction, values were assumed (between 0-1). Detailed
calculations are shown in the attached excel. As an example, for = 0.95, was estimated
according to Equation (1) as shown below.

3
 1
= = 20
1 0.95

The curve showing as a function of was generated by use of excel and it is given in
Figure 1.

1000
900
Xn (Number average degree of

800
polymerization), -

700
600
500
400
300
200
100
0
0,8 0,82 0,84 0,86 0,88 0,9 0,92 0,94 0,96 0,98 1
p (Extent of reaction) ,-

Figure 1. Number-average degree of polymerization versus extent of reaction.

2.3. Task (c): Reaction carried out in a closed system

This task required determination of the degree of polymerization and the extent of the reaction
when the reaction is performed in a closed system i.e. without removal of the by-product water.
The equilibrium constant for the polymerization reaction was given as equal to 200.

At this point lets consider the polymerization reaction in Scheme I as a generic equilibruim
reaction in the equation below, where A and B react to form C and D. Here A & B represent
adipic acid and hexamethylene diamine respectively. Similarly, C& D represent the polyamide
product and the by-product water respectively.

+ + 2

For this reaction, let =1 and the equilibrium constant can be described as in Equation (2).

[][]2 [][]2
= = (2)
[][] []2

4
Where [A], [B], [C] & [D] are concentrations of respective components. It is important to note
here that the reactants are assumed equimolar as per the given task.
From literature [3], the Equilibruim constant from Equation (2) can be expressed in terms of extent
of reaction as follows:

[] = []0 = 0,
[] = []0 = []0

[] = []0 = []0

[] = [] = []0 []0 = []0 (1 )

[]0 ([]0 )2 2 []0 3 2 []0

= = = (3)
([]0 (1 ))2 []0 2 (1 )2 (1 )2

Assuming here that []0 is equal to 1 M (or considering equimolar reactants and products) in
order to get rid of the concentration term, then Equation (3) reduces to Equation (4).

2
= (4)
(1 )2

Further simplification of Equation (4) gives Equation (5) which describes the extent of reaction
in terms of the equilibrium constant. [3]
1
2
= 1
(5)
1+ 2

Thus from Equations (1) & (5) the number-average degree of polymerization can be
determined as shown in Equation (6). [3]

1
= 1 + 2 (6)

For this task, & were calculated as below,

200
= = 0.9334
1 + 200

= 1 + 200 = 15.14

5
2.4. Task (d): Reaction carried out with removal of water
In this case an open system was considered and the task was to solve for the concontration at
which the observed degree of polymerization was equivalent to 200 when the initial
concentration of the acid was 2 M. From literature [3], the equilibruim constant of this system can
be decribed by Equation (7).

[] 1 [] 1 1 []
= = = ( 1) (7)
[]0 (1 )2 1 1 []0 1 1 []0

where [] represents water concentration at quilibrium. From Equation (1) and (7) the
concentration of water is deduced accordingly as shown in Equation (8). [3]

[]0
[] = (8)
1)
(

Equation (6) was used to solve this task as demostrated below.

2 200
[] = = 0.01005
200 (200 1)

Thus in order to achieve a degree of polymerization of 200, water concentration must be lowered
to 0.01005 .

2.5. Task (e): Number-average molecular weight

of polymer in
This task required determination of the number-average molecular weight
can be described by Equation (9). [2]
task (d). From literature,

0
= 0 =
(9)
1

Using Equation (9), the number-average molecular weight was calculated as shown below.

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3. Remarks

[1]
For task(a), in literature some sources indicate a polymer to water mole ratio of 1:2 whereas
others show 1:1 mole ratio [4] respectively. In this work, tasks (c) & (d) were solved by assuming
an equimolar mole ratio between polymer product and by-product water.

References

1. Condensation (Step-Reaction) Polymerization, [online], available:

http://61.188.205.38:8081/hxgcx/polymer/UploadFiles/swf/%E8%B5%84%E6%96%99%E5%
BA%93/Polymer%20Science%20and%20Technology/8939_CH06.pdf [February 7, 2017]
2. Lecture notes (2017), CHEM-E2145 Polymer Reaction Engineering, Aalto University
3. Step growth polymerization, [online], available: https://ocw.mit.edu/courses/chemical-
engineering/10-569-synthesis-of-polymers-fall-2006/lecture-notes/lec02_09082006.pdf
[February 7, 2017]
4. Polymerization reactions: step-growth polymerization, [online], available:
http://gozips.uakron.edu/~wwschlo/polyfiles/poly104.pdf [February 7, 2017]