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Synthesis of PMMA

The document summarizes an experiment to synthesize poly(methyl methacrylate) (PMMA) via emulsion polymerization. Potassium persulfate was used as an initiator and sodium dodecyl sulfate as a surfactant. Nuclear magnetic resonance spectroscopy and size exclusion chromatography were used to characterize the resulting PMMA. The NMR spectra confirmed the polymer structure, but size exclusion chromatography found the number average molecular weight was 775,469 Daltons, higher than the target of 30,000 Daltons, demonstrating the difficulty of molecular weight control in emulsion polymerization.

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Te-greg Miller
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1K views

Synthesis of PMMA

The document summarizes an experiment to synthesize poly(methyl methacrylate) (PMMA) via emulsion polymerization. Potassium persulfate was used as an initiator and sodium dodecyl sulfate as a surfactant. Nuclear magnetic resonance spectroscopy and size exclusion chromatography were used to characterize the resulting PMMA. The NMR spectra confirmed the polymer structure, but size exclusion chromatography found the number average molecular weight was 775,469 Daltons, higher than the target of 30,000 Daltons, demonstrating the difficulty of molecular weight control in emulsion polymerization.

Uploaded by

Te-greg Miller
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Synthesis of Poly(methyl methacrylate) via

Emulsion Polymerization
By
Greg Miller, Josh Burton and Mohammad Tasooji

Experiment was performed 9-14-2012


Submitted 10-5-2012

Introduction
Poly(methyl methacrylate), or PMMA, is a mass produced polymer with
trade names that include Plexiglas and Lucite; PMMA is also used in latex
paints and as a viscosity modifier for lubricating oils. Poly(methyl
methacrylate) is known to have a glass transition temperature near 100C.
The structure of PMMA is shown in Figure 1. Potassium persulfate, K2S2O8, is
used as a radical initiator; potassium persulfate has a decomposition rate
constant, kd, of 9.6*10^5 s^-1. Dodecyl sulfate is used as the surfactant or
emulsifying agent is this reaction.

Figure 1. Structure of PMMA


Emulsion is an important technique of water born heterophase
polymerization; emulsion polymerization is industrially attractive because
the bulk of solvent is water, which also helps control reaction temperature. In
emulsion polymerization, free radicals are generated in the aqueous phase
and propagated with monomer within the hydrophobic core of micelles. The
micelles are formed from an amphiphilic surfactant and water; the level of
surfactant must be greater than its critical micelle concentration for micelles
to form1. The rate of an emulsion polymerization is independent of the rate
of generation of radicals by initiator but rather is dependent on the number
of polymer particles in a cubic centimeter of the aqueous phase and the
monomer concentration in the polymer particles2. The four most important
factors in determining the rate of an emulsion polymerization are the
propagation rate coefficient, the latex particle concentration, the monomer
concentration in the latex particles, and the free-radical concentration in the
latex particles; propagation of polymers by emulsion polymerization is
diffusion controlled if the reaction is performed below the glass-transition
temperature of the corresponding polymer3.
Experimental
Goal
The objective of this experiment is to synthesize and characterize
30,000 g/mol poly(methyl methacrylate) via an emulsion polymerization.
Materials
Recipe
Deionized Water
Methyl Methacrylate
Sodium Dodecyl
Sulfate

Quantity
18 mL
9.64 mL
0.2044 g
2

Potassium Persulfate

0.1040 g

The formulation was based on a recipe by Flory but scaled down by 10% for
our purposes2.

Procedure
The oil bath was heated to 70-75C and the heat is maintained by the
use of a thermo-couple. Next 18 mL of deionized water was added to a 100
mL single-neck round bottom flask and a rubber septum was attached to the
flask; the water was purged with N2 gas for 10 minutes. The methyl
methacrylate monomer was cleansed of hydroquinone by running it through
a column filled with Al2O3 powder. The dodecyl sulfate was then added to the
water and stirred for five minutes to allow the surfactant to reach the critical
micelle concentration. Next the methyl methacrylate monomer was added
to the flask with a syringe and the mixture was stirred for five minutes to
allow the monomer to penetrate into the micelle cores. The potassium
persulfate initiator was dissolved in 5 mL of water by sonication and was
then introduced into the reaction mixture. The solution was observed to be
very cloudy. After two hours, the reaction was very opalescent. The reaction
is allowed to proceed for three hours. Two different methods were employed
for recovery of the polymer from the emulsion. Method A involved
precipitation into a concentrated solution of aluminum sulfate. The
precipitated product was vacuum-filtered and washed with water and
methanol to remove residual salts and surfactant. Method B involved
precipitation into a concentrated potassium chloride solution. The
precipitated product was vacuum-filtered and washed with methanol to
remove residual surfactant. Both vials of polymer were placed into a 70C
vacuum oven for 24 hours to dry any remaining solvent.
The product was analyzed by nuclear magnetic resonance using an
Agilent MR4 NMR at 400 MHz. Additionally, molecular weight analysis was
performed by size exclusion chromatography.
Results and Discussion
Nuclear Magnetic Resonance Spectroscopy
The NMR spectra for the poly(methyl methacrylate) sample is shown
below in Figure 2.

Figure 2. Integrated NMR Spectra for PMMA.


The NMR spectra in Figure 2 is consistent with known NMR data of
poly(methyl methacrylate). From the chemical shifts at 0.8 ppm and 1.0
ppm it can be determined that the majority of the product has Syndiotactic
and Atactic conformations4.
Size Exclusion Chromatography
Number-average molecular weight (Mn) and polydispersity index (PDI)
of the polymeric materials were measured using a gel permeation
chromoatography (GPC) system consisting of a Waters Alliance 2690
separation module, and three Styragel HR columns (5 m bead size)
connected in series. Sample concentrations were 25 mg of polymer/ mL of
solvent and the flow rate was 1.00 mL/ min. The method involves comparing
the results to polystyrene S.E.C. data of known molecular weights and it is
assumed that 100% mass recovery from the columns was acheived. The
chromatograph for the PMMA sample is shown below (Figure 3). The MN of
the sample was found to be 775,469 Daltons.

Figure 3. Size Exclusion Chromatograph for Poly(methyl


methacrylate).

The targeted molecular weight of 30,000 g/mole was not achieved


successfully. Molecular weight control is notoriously hard to accomplish in
emulsion polymerizations; very high molecular weights often prevail5. Two
kinetic theories predominate: Smith-Ewart kinetic model and Fitch-Tsai kinetic
model; the kinetic models for emulsion polymerizations have very hard
parameters to accurately predict such as the number of latex particles per
unit volume of water and the average number of free radicals per particle6.
Conclusion
Emulsion polymerization involves the nucleation and growth of particle
nuclei with monomer inside; a heterogeneous reaction system is created in
which mini bulk polymerizations occur within the particle nuclei as free
radicals are diffused into the latex particles. Very high molecular weight
poly(methyl methacrylate) with primarily syndiotactic and atactic
conformations was produced with via emulsion polymerization. The targeted
molecular weight was surpassed by an order of magnitude as molecular
weight control is difficult in emulsion polymerization.

References
(1)
Arora, P.; Jain, R.; Mathur, K.; Sharma, A.; Gupta, A. African Journal of
Pure and Applied Chemistry 2010, 4, 5.
(2)
Flory, P. Principles of Polymer Chemistry; Cornell University Press:
Ithaca, New York, 1953.
(3)
Maxwell, I.; Verdumen, E.; German, A. Makromol. Chem. 1992, 193, 24.
(4)
Kitayama, T.; Zhang, Y.; Hatada, K. Polymer Bulletin 1994, 32, 439.
(5)
Arshady, R. Colloid and Polymer Science 1992, 270, 7107.
(6)
Chern, C. S. Progress in Polymer Science 2006, 31, 443.

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