In the Laboratory
Polymerization and Characterization of PMMA W
Polymer Chemistry Laboratory Experiments for Undergraduate Students
Caroline Duval-Terrié and Laurent Lebrun*
UMR 6522 CNRS, Université de Rouen – Faculté des Sciences, 76821 Mont-Saint-Aignan Cedex–France,
*laurent.lebrun@univ-rouen.fr
In this experiment third-year undergraduate chemistry
students (1) prepare polymethylmethacrylate (PMMA), one
of the best-known industrial polymers. First, the free radical
polymerization of methyl methacrylate (MMA) monomer
with various ratios of initiator and monomer (I:M) are ex-
amined. By analyzing their polymeric products with size ex-
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clusion chromatography (SEC), the students can verify the
kinetics scheme of the radical chain polymerization. Second,
anionic chain polymerization is examined to show the influ-
ence of the polymerization process on the stereochemistry of
the chain. The tacticity can be investigated by proton nuclear
magnetic resonance spectroscopy (1H NMR) and the influ-
ence on the glass transition temperature (Tg ) can be mea-
sured by differential scanning calorimetry (DSC).
PMMA belongs to the acrylic polymer family and is
known by trademarks such as Lucite, Perspex, Oroglas,
Goldglas, Altuglas, or Plexiglas. The production of PMMA
in the world is over 6 × 105 tons per year (2) and is sold at
∼$5 per kg. This polymer is amorphous and gives thermo-
plastic materials that are hard, rigid, and brittle at room tem-
perature. PMMA is more transparent and less brittle than
conventional glass with a lighter weight and it is easy to mold
into a variety of shapes. PMMA shows a wide variety of uses
as glass replacement material in cars and aircraft (light clus-
ters, dashboards, canopies, port-holes), in urban furnishing
(verandas, antinoise walls, shop signs, display units, light dif-
fusers, reflectors) and in medical applications (contact lenses,
lenses, teeth, hospital incubators) (2). Surgical-grade PMMA
H3C R H 3C R H3C R
isotactic
H H H H
H3C R R CH3 H3C R
syndiotactic
H H H H
H 3C R H3C R R CH3
atactic
H H H H
Figure 1. Stereoregularity of PMMA: isotactic, syndiotactic, and
atactic.
www.JCE.DivCHED.org • Vol. 83 No. 3 March 2006
is used as bone cement by self-polymerizing during curing
(3). PMMA is also used in the manufacture of bathtubs,
hand-wash basins, dashes, optical fibers, adhesives, and glues
(PMMA兾MMA).
Theory
Chain addition polymerization occurs by the stepwise
addition of monomer units to an active site on the growing
chain. This is possible because of the opening of a double
bond or a cycle on the monomer. The presence of an elec-
tron withdrawing group (⫺COOCH3) on MMA monomers
stabilizes either the free radicals or the carbanions and thus
favors either the free radical or the anionic polymerizations.
Radical Polymerization
The chain reaction involves four steps: initiation, propa-
gation, termination, and transfer. The initiation is illustrated
with 2,2´-azo-bis-isobutyrylnitrile (AIBN) as initiator and the
transfer reaction to the monomer is shown in Scheme I.
Anionic Polymerization
The steps of anionic polymerization are similar to those
of free radical polymerization. The initiator is a strong base,
such as n-butyllithium (n-BuLi), that reacts with the double
bond of the monomer (nucleophilic addition) (Scheme II).
At the end of the polymerization, each macromolecule keeps
its living end as long as there are no protic impurities. This
system is usually called “living anionic polymerization” be-
cause there is no termination step. At the end of the synthe-
sis, HCl (or NaCl) is added to deactivate the active center.
Tacticity
Tacticity is the term used to describe the configuration
of polymer chains. Three distinct structures can be obtained.
Isotactic is an arrangement where all substituents are on the
same side of the polymer chain (Figure 1). A syndiotactic poly-
mer chain is composed of alternating stereocenters and an
atactic polymer is a random combination of the groups.
Thermal Properties
The type of tacticity has a great influence on the physi-
cal properties of the material. From a thermodynamic point
of view, the glass transition temperature, Tg, is one of the
most important parameters for characterizing a polymer (4).
Tg can be interpreted as the temperature where the segments
of the macromolecule chains begin to move. At Tg, short
chain segments undergo rotation, translation, and diffusion
motions. Below Tg, an amorphous polymer has the charac-
teristics of a glass, while it becomes leathery and rubbery
above Tg (4).
• Journal of Chemical Education 443
In the Laboratory

Initiation

CH3 CH3 CH3 Scheme I. Free radical polymerization of MMA

H3C C N N C CH3 2 H3C C ⴙ N2 with AIBN as the initiator.
CH3 CH3 CN

CH3 CH3 CH3

CH3
H2C C H3C C C C
H 3C C ⴙ H2
C OCH3 C OCH3
CN
CN
O O

Propagation
CH3 CH3 CH3 CH3 CH3 CH3 CH3
H3C C C C C C ⴙ H2C C H3C C C C C C
H2 H2 H2 H2
C OCH3
CN COOCH3 COOCH3 CN COOCH3 COOCH3
n O n+1

Termination
Combination

CH3 CH3 CH3 CH3 CH3

C C CH2 C ⴙ C C CH2 C C C
H2 H2 H2
COOCH3 COOCH3 COOCH3 COOCH3 COOCH3
m n m+n+2

Disproportionation

CH3 CH3 CH3 CH3

C C CH2 C ⴙ C C CH2 C
H2 H2
COOCH3 COOCH3 COOCH3 COOCH3
m n

CH3 CH3 CH3 CH3

C C CH2 CH ⴙ C C CH C
H2 H2
COOCH3
COOCH3 COOCH3 COOCH3
m n

Transfer
CH3 CH3 CH3 CH3 CH3 CH3
C C CH2 C ⴙ H2C C C C CH2 CH ⴙ HC C
H2 H2
COOCH3 COOCH3
COOCH3 COOCH3 COOCH3 COOCH3
n n

Initiation

Scheme II. Anionic polymerization of MMA with

H3C C C C Li H3C C C C ⴙ Li
H2 H2 H2 H2 H2 H2 n-BuLi as the initiator.

CH3 CH2

H3C C C C ⴙ H 2C C H3C C C C C C
H2 H2 H2 H2 H2 H2 H2
COOCH3 COOCH3

Propagation
CH3 CH3 CH3 CH3 CH3
H 3C C C C C C C C ⴙ H 2C C H3C C C C C C C C
H2 H2 H2 H2 H2 H2 H2 H2 H2 H2
COOCH3
COOCH3 COOCH3 COOCH3 COOCH3
n n+1

Termination
CH3 CH3 CH3 CH3
H3C C C C C C C C ⴙ H H3C C C C C C C CH
H2 H2 H2 H2 H2 H2 H2 H2 H2 H2
COOCH3 COOCH3 COOCH3 COOCH3
n n

444 Journal of Chemical Education • Vol. 83 No. 3 March 2006 • www.JCE.DivCHED.org

 In the Laboratory

Experimental Procedure Table 1. Yield and SEC Analysis

of the Free Radical MMA Polymerizations
The students work in pairs. The instructor chooses the [I]/ Yield Mave,n/ Mave,W/
D
polymerization reaction to be performed (radical or anionic) (10᎑3 mol L᎑1) (%) (g mol᎑1) (g mol᎑1)
and the technique for characterizing the PMMA, depending 2.2 0 — — —
on the apparatus available in the laboratory. The explicit de-
4.7 11 7230 25300 4.5
tails of the experimental procedures for the polymerization
and for the characterization of the polymers are given in the 8.8 4 5050 22700 4.5
Supplemental Material.W Each group of students uses a dif- 11.1 23 6620 18000 2.8
ferent I:M ratio for the radical polymerization and a differ- 22.2 40 5390 14500 2.7
ent quantity of THF for the anionic polymerization. The 33.2 51 3150 7240 2.3
students analyze a dry polymer previously synthesized by an- 55.4 56 4250 7200 1.7
other group during an earlier experiment. This analysis is
67.1 64 3360 6910 2.1
performed during the waiting time for the polymerization
(2 hours for the radical polymerization and 1.5 hours for the 94.2 77 3400 6300 1.9
anionic polymerization). NOTE: D = Mave,W/Mave,n.
The average molecular weight (Mave,n and Mave,W)1 and
the polydispersity D of the synthesized PMMA (D =
Mave,W兾Mave,n) are determined with SEC. The number of
units per chain (xave,n) is deduced from the relationship Mave,n
Table 2. Study of the Free Radical MMA Polymerizations
= M0(xave,n), where M0 = 100 g mol᎑1 for PMMA. The tac-
ticity of the PMMA samples are investigated with 1H NMR. No Transfer Rxn With Transfer Rxn
I:M/ Exp
The influence of the tacticity on the thermal properties (Tg) (10᎑3) xave,n Calc α Calc
α
of the polymer is assessed by DSC. At the end of the class, xave,n0 xave,n
the results are compared. 5.47 72.3 96.4 ᎑0.66 93.4 ᎑0.58
13.0 66.2 62.5 0.11 61.2 0.15
Hazards 26.1 53.9 44.2 0.36 43.6 0.40
39.1 31.5 36.1 ᎑0.29 35.7 ᎑0.27
MMA, toluene, THF, deuterated chloroform, and hep-
65.1 42.5 27.9 0.69 27.7 0.70
tane are toxic irritants and noxious. HCl is irritating to eyes
78.8 33.6 25.4 0.49 24.8 0.52
and skin. Toluene, heptane, and THF are highly flammable.
AIBN is explosive. n-BuLi causes burns, is spontaneously 110.7 34 21.4 0.76 20.8 0.77
flammable in air, and reacts violently with water, liberating
extremely flammable gases. The experiments must be done
under a fume hood protected by a pane of glass. The stu-
dents must use lab coats, safety goggles, and protective gloves xave,n values measured by chromatography were erroneous and
(nitrile or heat protective). Safety and hazards are discussed did not agree with the corresponding calculated values; con-
further in the Supplemental Material.W sequently, the α ratio obtained from the measured values was
near to zero or negative. The results also show that the trans-
Calculations and Comments fer reactions have a low influence on the number of units
per chain.
Free Radical Polymerization
Typical results obtained by groups of students are shown Anionic Polymerization
in Table 1. The quantity of AIBN initiator [I] influences the After assigning the 1H NMR peaks of their PMMA
yield of free radical polymerization. For the same monomer samples, the groups of students measured the peak areas and
concentration, the higher the initiator concentration, the calculated the ratio of isotactic, syndiotactic, and atactic seg-
higher the yield of the polymerization. Logically, high initia- ments (Table 3) (1H NMR spectra and explanations are given
tor concentrations give low molecular weights, a small num- in the Supplemental MaterialW). The anionic polymerization
ber of units per chain (xave,n), and low polydispersity of the of MMA monomer (without THF) gives highly isotactic ste-
chains. reoregular polymers. The spatial structure of the living end
The groups of students can apply the theoretical rela- governs the stereochemistry of the addition of the MMA
tions of the kinetics of the free radical polymerization (5, 6) monomer. The mechanism involves the counterion (Li+)
to analyze their results (see the Supplemental MaterialW). The blocking the last two units of the growing chain and the
calculated values xave,n0 (without transfer reaction), xave,n (with monomer (by their carbonyl groups). At each step, therefore,
transfer reaction), and the measured values xave,n (with trans- the geometry of the living end and the way the monomer
fer reaction obtained by chromatography) for each experi- approaches remain the same. The resulting sequence leads to
ment are given in Table 2. They can be compared to calculate an isotactic structure. When a polar solvent (THF) is added
the α ratio of termination by combination. For a constant to the reactive medium, the double coordination of lithium
monomer concentration, the quantity of AIBN initiator in- is decreased and the addition of monomer is less oriented.
fluences the termination. The higher the initiator concen- Syndiotactic structure is favored at low THF concentration
tration, the higher the termination by combination. Some and atactic structure is favored at higher THF concentration.

www.JCE.DivCHED.org • Vol. 83 No. 3 March 2006 • Journal of Chemical Education 445

In the Laboratory

Table 3. 1H NMR and DSC Analyses of PMMA kinetics of both polymerizations may be studied by using a
T y pe o f Sy ndiot act ic A t act ic Is ot act ic Tg / dilatometer and, in this way, orders of reaction and rate con-
Poly me rizat ion (%) (%) (%) °C stants can be calculated (8). An organometallic initiator of
the MMA anionic polymerization can be prepared in a prior
Ionic 11.0 09.2 79.8 48
experiment and examined (e.g., phenylmagnesium bromide
Ionic (2.5% TH F) 20.3 11.6 68.1 80 C6H5MgBr).
Ionic (5% TH F) 12.2 22.9 64.9 56 W
Supplemental Material
Ionic (10% TH F) 09.6 28.9 61.5 42
Instructions for the students, notes for the instructor,
Radical 55.5 28.6 15.9 97 kinetics of free radical polymerization, and NMR spectra are
available in this issue of JCE Online.

Note
The free radical polymerization of MMA monomer gives
more syndiotactic polymers owing to the steric and electro- 1. Polymer weights can be expressed as either the number-
static repulsions between the (⫺COOCH3) groups (Table 3). average molecular weight, Mave,n, or the weight-average molecular
The Tg of PMMA significantly varies according to its weight, Mave,W. An article in this Journal describes these terms and
tacticity (Table 3). The molecular structure of the chain and gives sample calculations (9).
the orientation of the side groups influence Tg. In syndio-
tactic chains, the bulky substituents (⫺COOCH3) are dis- Literature Cited
tributed on both sides of the backbone. They behave as an
anchor between the chains (7). Consequently, they slow down 1. Jefferson, A.; Phillips, D. N. J. Chem. Educ. 1999, 76, 232.
the motions of the chain segments during heating; this in- 2. Chisholm, M. S. J. Chem. Educ. 2000, 77, 841.
creases Tg. When the bulky substituents are on the same side 3. Vallo, C. I. Polym. Int. 2000, 49, 831.
of the polymer chain (isotactic) or highly randomly distrib- 4. Sandler, S. R.; Karo, W.; Bonesteel, J.-A.; Pearce, E. M. In
uted (atactic), they do not have this function, so the Tg is Polymer Synthesis and Characterization: A Laboratory Manual;
lower. Thus, the Tg of ionic PMMA is low. Acadamic Press: New York, 1998.
5. Morton, M. J. Chem. Educ. 1973, 50, 740.
Conclusions 6. McGrath, J. E. J. Chem. Educ. 1981, 58, 844.
7. Macrogalleria Level 3. http://www.pslc.ws/macrog/level3.htm
Various modifications can be applied to this experimental (accessed Jan 2006). The students should read the part con-
procedure. For example, with minor modifications, the free cerning the glass transition.
radical polymerization procedure of MMA may be applied 8. Martin, O.; Mendicuti, F.; Tarazona, M. P. J. Chem. Educ.
to other common vinyl monomers such as styrene, vinyl ac- 1998, 75, 1479.
etate, vinylidene chloride, acrylonitrile, and acrylamide. The 9. Snyder, D. M. J. Chem. Educ. 1992, 69, 422.

446 Journal of Chemical Education • Vol. 83 No. 3 March 2006 • www.JCE.DivCHED.org