EXPERIMENT 5

Bulk Polymerization of Polyurethane

5.0 Objective:

To synthesize polyurethane by bulk polymerization technique and to examine the

physical properties of the polymer.

5.1 Introduction:

The bulk addition polymerization is the simplest of all polymerization processes. Bulk
polymerization is the conversion of monomer into a polymer without the aid of a solvent.
A bulk addition polymerization is a homogeneous system with an organic initiator.

Polyurethane is one of the important classes of synthetic polymers used as elastomers,

surface coating or as adhesives and have been widely used as biomedical materials

A urethane linkage is produced by reacting an isocyanate group, -N=C=O with a

hydroxyl (alcohol) group, -OH. Polyurethanes are produced by the polyaddition reaction
of a polyisocyanate with a polyalcohol (polyol) in the presence of a catalyst and other
additives. In this case, a polyisocyanate is a molecule with two or more isocyanate
functional groups, R-(N=C=O) and a polyol is a molecule with two or more hydroxyl
functional groups, R'-(OH). The reaction product is a polymer containing the urethane
linkage, -NHCOO'-.
O H H O
|| | | ||
HO-R-OH + O=C=N-R'-N=C=O  -- [ -O-R-O-C-N-R'-N-C-] --
Polyol Isocyanate polyurethane

where R and R’ are carbon chain and aromatic ring respectively.

In this experiment, polyurethane is prepared using aromatic isocyanates,

diphenylmethane diisocyanate (MDI) and polyester polyols; poly(tetramethylene glycol).
1,4-butanediol (1,4-BDO or BDO) is used as chain extenders that separate the hard and
the soft domains of polyurethanes. The high molecular weight polyols form soft
segments that are mobile and are normally present in coiled form, while the hard
segments, which are formed from the isocyanate and chain extenders, are stiff and
immobile.

Formation of polyurethane :

2 + HO-(CH2-CH2-O)n-H

4,4’ diisocyanate , (MDI) Poly(tetramethylene glycol)

5.2 Materials:

4,4’ diisocyanate (MDI)

Poly(tetramethylene glycol)
1,4 Butanediol
No. 34, emulsion release agent (Dow Corning)

5.3 Apparatus:

Vacuum oven
Hot plate
2 piece of 250 ml beaker
High torque stirrer (with metal blade and shaft)
Metal thermometer
Digital timer
1 piece of disposable aluminum pan (8” x 10” x 1” depth)

5.4 Safety Precaution:

Isocyanates are strong skin irritants and must be handled with proper
precautions. Safety glasses and gloves must be worn at all times.
5.5 Preparation

a) Dry the polymeg in vaccum oven for 15 minutes at (110-120) ºC.

b) Coat the disposable aluminum pan with a mixture of equal parts of water and No.
34 emulsion release agent, and dry it in an oven at 110 ºC.

5.6 Procedure:

Beaker 1 (250 ml) Beaker 2 / MDI Speed I* Speed II*

Weigh 102.2 g ( 97 ml) 50.0 g (40.4 ml) Medium High
polymeg and 9.0 g (9 ml) 52.5 g (42.4 ml) Medium High
1,4 butanediol 55.0 g (44.5 ml) Medium High
Note: * Medium speed = turn the stirrer knob to 90°
High speed = turn the stirrer knob to 270°

a) Set up the stirrer in the MDI beaker.

b) With continuous stirring, add the polymeg-bitanediol mixture to MDI. Increase the
power of the stirrer as the viscosity of the mixture rises sharply.
c) Measure and record the reaction temperature every 15 second.
d) Stop the agitation after 4 minutes or when 2 consecutive temperature reading are
the same.
e) Remove the stirrer and pour the contents into the pre-coated aluminum pan.
f) Spread the polymer to a thin layer and quickly cool the pan in ice water.
[Caution! Do not splash water on the hot polymer]
g) Weigh the polyurethane obtained and record the weight of all the polyurethane
obtained from other groups that used different weight of MDI.
h) Observe the structure of polyurethane under a microscope.

5.7 Data analysis:

a) Tabulate and calculate the weight of the polymer obtained from various
amount of MDI used. [Obtain results from other groups]
b) State the physical properties of your polyurethane.
c) Describe the structure of polyurethane that is observed under microscope.
5.8 Questions:

a) Give the structure of the polyurethane prepared from this experiment.

b) Give the advantages of this type of polymerization process in the preparation of a
polymer.
c) What are the limitations of this type of polymerization process.
d) State the disadvantage(s) of the polymer obtained from this polymerization
process.
 CHM 572
EXPERIMENT 5
REPORT SHEETS

Name :

Group Members : 1.
2.
3.

Date of Experiment :
5.0 Objective:
Write the objective of the experiment:

5.1 Procedure:
Summarized your procedure in a form of flow chart.
5.2 Results and Discussions:

a) Tabulate and calculate the % yield of the polymer obtained from various
amount of MDI used. [Obtain results from other groups]

Weight of MDI used Weight of Polyurethane % yield

(g) (g)

b) Calcualte the % urethane linkages of the polymer from each group.

c) Plot a graph of temperature versus time for the polymerization of your
polyurethane. Discuss your result.
 d) State the physical properties of your polyurethane.

e) Describe the structure of polyurethane that is observed under microscope.

5.3 Conclusions:
Conclude or give any comments on the results obtained from the experiment.
5.4 Questions:

a) Give the structure of the polyurethane prepared from this experiment.

b) Give the advantages of this type of polymerization process in the preparation of a

polymer.

c) What are the limitations of this type of polymerization prosess.

d) State the disadvantage(s) of the polymer obtained from this polymerization

process.