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POLYMER
INDUSTRY
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:
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
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:
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)
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
Density, = Mass, M
Volume, V
0.936 = Mass, M
10
= 8.8200 g x 100%
9.3600 g
= 94.23 %
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:
C O O C
O O
( benzoyl peroxide )
initiator
2 C O
2 + 2 CO2
O
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
X X
X X
Disproportionation
H H H H
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. 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