CHM 3102

POLYMER
INDUSTRY

Name : Chang Siew Yin

Matric number : 116094
Programme : BS(H) Industrial Chemistry

Name : Chen Wai Soon

Matric number : 115093
Programme : BS(H) Industrial Chemistry

Title : Synthesis and characterization of

polymethylmethacrylate
Number of experiment :7

Date : 13th September 2005

Laboratory : Makmal Pengajaran 4

Demonstrator : Lim Chee Siong
EXPERIMENT: 7

TITLE:
Synthesis and characterization of polymethylmethacrylate

OBJECTIVES:
1) To synthesis polymethylmethacrylate (PMMA) from its monomer -
methylmethacrylate (MMA)
2) To understand the process and mechanism of free radical polymerization
3) To understand the reaction of polymethylmethacrylate
4) To know the characterization of polymethylmethacrylate
5) To determine the percentage of conversion and percentage of recovery of
methylmethacrylate

INTRODUCTION:
Methylmethacrylate (MMA) is a resin which is cured with a small amount of peroxide.
MMA can be soft (like contact lenses) or hard (like Plexiglas). MMA can be installed in
sub-zero temperatures! This is simply not possible with conventional epoxies. MMA has
a strong odor and is not for use where building personnel might be exposed to the vapors.
Therefore, good ventilation is necessary for a proper cure.

MMA (and most vinyl monomers) is supplied with a small amount of inhibitors, which is
added to prevent polymerization during shipping and storage. Usually the inhibitor is
removed prior to use. This can be accomplished by distillation, chromatography (like
thin-layer chromatography) or by extraction with base (the inhibitor is an organic acid).
MMA can purified by chromatography with alumina then polymerizing it using benzoyl
peroxide as the initiator and resulting the using viscometry and infra-red spectroscopy.
Polymethylmethacrylate (PMMA) or poly(methyl-2-methylpropanoate), a synthetic
resin belonging to the family of polymeric organic compounds, is manufactured by bulk,
solution, suspension, and emulsion polymerization of MMA monomer, usually in
aqueous suspension. The resin has excellent transparency which takes a good gloss with
the property of weather resistance, high surface hardness and coloring property. It is used
as a replacement for glass. Its application includes the semi-finished products of
automotive parts, electronic parts, illuminated display sheet for advertising, building
materials and LCD (Liquid Crystal Display) plates.

Commonly, PMMA is a vinyl polymer, made by free radical vinyl polymerization from
the monomer methyl methacrylate.

There are two main approaches to the polymerization of the monomer in the
monomer/polymer combination, and materials are formulated appropriately:

1. By heating to ca 70C (Heat cured PMMA)

2. By chemical activation at room temperature (Cold curing, or auto polymerizing
PMMA)

Since PMMA is non-crystalline, appropriate solvents will be absorbed by and swell the
polymer. The effect is purely of physical significance as a chemical reaction is not
involved. Thus, the value of Tg for the polymer is reduced. When this value is lowered to
below room temperature, the polymer or monomer combination acts as a gel (cf
hydrocolloids) and may be shaped, as desired. In practice, the combination of polymer
with liquid results in following sequence of effects:
i. Wet sand stage
ii. Stringy stage
iii. Gel (full dough) stage
iv. Elastomeric stage

Polymerization of MMA can be activated by the unstable organic peroxide, benzoyl

peroxide (white crystalline solid) which decomposes to form phenyl free-radicals at a
temperature of ca 70 C. This can be achieved through the use of dry heat, as in an oven,
or via a heated water bath. Once polymerization has been initiated, it is important that an
excessive temperature rise does not take place in the dough because the polymerization is
exothermic. If this temperature exceeds the boiling point of the monomer (100.3 C under
1 atm pressure, but may be higher under processing conditions), the monomer will
evaporate such that the processed will feature gaseous porosity. This is characterized by a
micro porosity evident at the bulkier where the temperature rise has been greatest.

The average molecular weights of these polymers have not been determined, but they are
thought to be fairly low (10s thousands). The primarily goal of this project is to modify
the existing procedure to give both a higher percent conversion and a higher average
molecular weight as determined by solution viscometry. The secondary goal is to get a
decent approximation of the molecular weights of the polymers by comparing their
viscosities to those of some PMMA samples of know molecular weight.

These are 5 laboratory periods scheduled for completion of this project. In order to
successfully complete this, we will have to accomplish the following:
1. Synthesis of PMMA using given procedure including purification and drying of
polymer and determination of percent conversion.
2. Determine solution viscosity of this PMMA sample in a solvent of our choice
(subject to availability and safety considerations).
 3. Generate a viscosity versus molecular weight curve using the supplied PMMA
samples of known molecular weight.
4. Develop at least 2 different modified synthetic procedure based on kinetic
considerations, perform these procedures and determine percent conversions.
5. Measure the solution viscosities of these materials.
METHODOLOGY:

10ml of MMA is put in a test tube.

1 drop of N, N-dimethylaniline and 0.1g of benzoyl peroxide is added to the same test
tube.

This mixture is placed in boiling water bath.

At 3 minutes intervals, 1 drop of the hot reaction mixture is transferred to a test tube
containing 10ml of methanol and noted whether it dissolves.

The change in solubility as the molecular weight increase during the reaction is observed.

After 15 minutes, the tube is cooled and the polymer is dissolved in 10-15ml of acetone.
The polymer with vigorous stirring is poured into a beaker containing 100ml of distilled
water.

The precipitate polymer by vacuum filtration is collected.

The polymer is dried and the product is examined.

The percent of conversion is determined.
RESULT:
Solubility in methanol:

Time/min 0 3 6 9 12 15
Not soluble Not soluble Not soluble
Very Quite Quite (precipitate (precipitate (precipitate
Solubility in white in white
soluble soluble soluble in white
colour) colour) colour)

The mass of the reaction yield:

Mass (g)
Filter paper + reaction yield 9.159
Filter paper 0.339
Reaction yield 8.820
CALCULATIONS:
Molecular mass of MMA with the molecular structure such as follows is

H
CH3

C C

C O
H

OCH3

= 5 (12.01) + 8 (1.01) + 2 (16.00)

= 100.13 g/mole

Density of MMA, = 0.936 g/cm3

From the equation of

Density, = Mass, M
Volume, V

Density, = Mass, M
Volume, V
0.936 = Mass, M
10

Theoretical mass of MMA = 0.936 x 10

= 9.3600g

So, the percentage of yield or percentage of conversion of MMA to PMMA

= Experimentally mass of MMA x 100%
Theoretical mass of MMA

= 8.8200 g x 100%
9.3600 g
= 94.23 %

Percentage of recovery = (100 94.23) %

= 5.77%
DISCUSSION:
In this experiment, polymethylmethacrylate (PMMA) was produced from the monomer
of methylmethacrylate (MMA) through the process known as free radical addition
polymerization. Benzoyl peroxide is used as an initiator. The mixture is placed in a
boiling water bath to enhance the reaction rate. The whole experiment is conducted in
fume cupboard.

From the result, the mass of the yield is 8.820g. This mass value contributes to the
percentage of conversion to 94.23% and the percentage of recovery is 5.57%. The low
percentage of recovery might be due to termination of polymerization at high
temperatures. PMMA terminates entirely by disproportination at polymerization
temperature above 60C, which is lower than boiling water temperature at 100C.
Besides that, the slightly brownish colour of the polymer obtained may be caused by
impurities in the sample as PMMA is naturally transparent and colourless

The first reaction in the initiation step involves benzoyl peroxide undergoing homolytic
cleavage to form two benzoyloxy radicals. The benzoyloxy radical subsequently form
benzene radicals and carbon dioxides. In the second reaction of the initiation step, each
benzene radicals react with a molecule of MMA to form a benzylic radical. The initiation
step involving benzoyl peroxide and MMA can be outlined as follows:

First Reaction in Initiation Step:

C O O C

O O
 ( benzoyl peroxide )
initiator

2 C O
2 + 2 CO2
O

Second Reaction in Initiation Step:

CH3

. + CH2 C

C O

OCH3

CH3

CH2 C .

C O

OCH3
OR
 CH3

. + CH2 C

C O

OCH3

CH3

.
C CH2

C O

OCH3

The chain radical formed in the initiation step is capable of adding successive monomers
to propagate the chain. This propagation step let the chain begins to grow as the benzylic
radical reacts with a molecule of MMA and form a new benzylic radical which then
reacts with another molecule of MMA adding the MMA and forming another new
radical. This process continues many times as the polymer chain lengthens. Once started,
the rate of reaction is relatively high for a chain formation. The propagation reaction
continues until it reacts in a termination reaction or until it uses up all the monomer
molecules in the reaction mixture. Propagation would continue until the supply of
monomer was exhausted electron covalent bond with loss of radical activity. This
tendency is compensated for in radical polymerization by the small concentration of
radical species compared to monomers. The propagation step can be outlined as follows:

CH3 CH3

CH2 .
OR
C + CH2 C

C O C O Common
OCH3 OCH3 termination
reaction
CH3 CH3
. .
combines
CH2 C C CH2
two radicals
C OC O from two
OCH3 OCH3
growing chains to form a longer chain to terminate both chain reactions. The termination
step can take place in two ways namely the combination or coupling and
disproportionation:

Combination or Coupling

H H H H

CH2C + CCH2 CH2C CCH2

X X
X X

Disproportionation

H H H H

CH2C + CCH2 CH2C H + C CH

X X
X X

The hydrogen transfer results in the formation of two molecules with one saturated and
one unsaturated end group. The termination steps that are involved in bulk
polymerization of PMMA are as shown as follows:
 CH3 CH3

CH2* C CH2 C .
+
C O C O

OCH3 OCH3
n

CH3 CH3

CH2* C CH2 C .

C O C O

OCH3 OCH3
n

CH3
CH3 CH3 CH3
CH*2 C CH2 CH2
C C CH*2 C
C O C O
C O C O
OCH3 OCH3
OCH3 OCH3
n
n

transfer agent
N,N - dimethylaniline

CH3

C CH2

C O

OCH3
n

Although the three steps of initiation, propagation and termination are both necessary and
sufficient for chain polymerization; other steps can also take place during polymerization.
As these often involve the reaction between a radical and a molecule, they are
conveniently so classified.
PRECAUTION STEPS:

a) All the apparatus and glass ware need to be rinsed with distilled water or with
the relevant chemicals to get rid of the impurities that may be in contact with
the apparatus.
b) Before weighing, the weighing machine plate should be wipe with tissue
paper and the door of the weighing machine should be close to evade air from
entering the weighing machine thus causing an unstable reading of mass on
the machine's scale.
c) The position of the eyes must be parallel with the lower meniscus of the
volume's mark on the cylinder when measuring the volume of the MMA
needed in order to avoid parallax error.
d) Vigorous stirring has to be applied when transferring polymer to 100ml water
fro homogening and better polymerization recovery.
e) Scrope out as much as possible from the test tube to avoid wastage and to
acquire higher percentage of yield.
f) During filtration, the beaker containing the polymer (PMMA) formed need to
be rinsed thoroughly with distilled water to prevent any waste of products.
g) The products should be completely dry before weighing.
CONCLUSION:
1. Polymerization of MMA to PMMA and benzoyl peroxide is used as initiator had
successfully produced.
2. Solubility in methanol:
Time/min 0 3 6 9 12 15
Not soluble Not soluble Not soluble
Very Quite Quite (precipitate (precipitate (precipitate
Solubility in white in white
soluble soluble soluble in white
colour) colour) colour)

3. The mass of yield obtained is 8.820g.

4. The percentage of conversion is 94.23%.
5. The percentage of recovery is 5.77%.
6. The colour of PMMA from experimentally is pale yellowish.
7. The equation of the reaction is :

8. The repeating units of PMMA:

REFERENCES:

1. Fressenden Ralph J and Joan S. Fressenden, Organic Chemistry, 6th edition,

Brock/Cole Publishing Company.
2. Fred W. Billmeyer, Textbook of Polymer Science, Second Edition, John Wiley
and Sons, Inc, 1971, pp: 256, 280 284, 410 - 412

3. http://plc.cwru.edu/tutorial/enhanced/files/polymers/synth/Synth.htm
4. http://www.psrc.usm.edu/macrog/pmma.htm
5. http://www.psrc.usm.edu/macrog/pmma.htm
6. http://www.goodfellow.com/csp/active/static/E/ME30.html
7. www.ucc.ie/ucc/depts/restorative/dextent/dchap4.pdf.
8. www.amershamhealth.com/medcylopedia/medical/volume%20III
%201/POLYMETHYLMETHACRYLATE%20Cement.Asp
9. http://www.plasticusa.com/pmma.html
10. www.indianplasticportal.com/pmma.html
11. http://mst-online.ndu/edu/mstonline/polymer/polymerization