Bulk polymerization of methyl methacrylate (MMA) to form

PMMA.

Aim: (a) To study the principle of bulk polymerization of MMA to PMMA initiated
by BPO, especially, investigate the temperature affection of the resulting polymers.
(b) To master the organic glass synthetic procedure.

Principle of the experiment

hang khong
The PMMA is one of the most important materials used in the aero industrial and
glasses for instruments applications, owning to the highly transparency, low density,
and good impact resistant as well as low temperature properties.
Other method such as solvent polymerization and emulsion polymerization can also
be used for synthesis of PMMA, however, some impurities are introduced and
resulting in a low transparent PMMA plate.

In this experiment, we shall study the free radical polymerization of MMA to PMMA
(Scheme 1). The bulky side groups make it totally amorphous resulting in high
transparency. vo dinh hinh

Scheme 1:The polymerization Scheme of PMMA

Bulk polymerization is polymerization of the monomer by adding the initiator to the

monomer itself to start the polymerization by thermal, light, irradiation and so on.
There are several advantages of bulk polymerization, including: the synthesis
procedure is simple, from monomer directly to the final product such as plate, rod or
pipelines and so on; small additives are needed during the polymerization procedure.
The disadvantage for bulk polymerization is the heat exchange during the
polymerization procedure (the Gibbs free energy for this polymerization reaction is
56.5 kJ/mol), the bulk polymerization happened very fast and heat was concentrated
in the local position, resulted in yellow product and some bulb remaining that affect
the quality of the polymer materials (Density of the monomer is 0.94 g cm-3; density
of PMMA is 1.19 g cm-3). So, the strictly controlling the polymerization temperature
and evolve the heat of the reaction is the key factor for this synthesis.
As the polymerization procedure going on, the viscosity of the system increase. At
this time, the polymer chain will have difficulty to diffusion but the monomer will not
affected too much, as a result, the initiation and propagation is still going on whereas
the termination is strongly restricted, resulting in an much enhanced reaction speed,
also called Trommsdorf effect. This effect is a common phenomenon in bulk
polymerization, which resulted in a much longer lifetime of polymer free radical
chain, much more concentrated heat, and higher dispersion of polymer chains.

Chemicals and Materials

MMA monmer (Already pruified), BPO initiator (recrystallized before use), vial (20
mL), three-neck-round-bottle flask (250 mL)

Polymerization Procedure

1: Synthesis of the prepolymer: Add MMA (120 mL) in a 250 ml three neck round
bottle flask equipped with stir bar, thermal meter and cap. The system was then added
0.1% BPO, after the addition, the system was stirred at room temperature till all of the
BPO was dissolved in MMA monomer. The system was then put into an oil bath with
temperature around 90 oC, till the viscosity of the solvent is a slightly higher than
glycerine, the solution was immediately immersed into cold water, the reaction was
dormant. The reaction time is almost 20 min.

2: Put the prepolymer to the module. Transfer carefully of the above prepolymers to
a 20 ml vial, you can add some artwork inside your own PMMA prepolymer.

3: Post polymerization of the prepolymer. Put the vials in an oven at 40 oC and kept
for 10 h then increased to 100 oC for 2 hs.

Some further questions:

1. Why prepolymer are used for this polymerization of PMMA, why the different
step of thermal polymerization are applied.
2: If there are some bulb in the system, can you explain why?
3: Can you calculated the shrinkage percent of this polymerization?
do co rut