Ind. Eng. Chem. Res.

2006, 45, 8539-8553 8539

Dynamic Modeling and Experimental Validation of the MMA Cell-Cast Process

for Plastic Sheet Production
Martı́n Rivera-Toledo,†,‡ Luis E. Garcı́a-Crispı́n,† Antonio Flores-Tlacuahuac,*,† and
Leopoldo Vı́lchis-Ramı́rez§
Departamento de Ingenierı́a y Ciencias Quı́micas, UniVersidad Iberoamericana, Prolongación Paseo de la
Reforma 880, México D.F. 01210, México, Departamento de Ingenierı́a Quı́mica, Facultad de Quı́mica,
UniVersidad Nacional Autónoma de México (UNAM) Conjunto E, Cd. UniVersitaria, México D. F. 04510,
México, and Centro de InVestigación y Desarrollo Tecnológico, AV. De Los Sauces 87-6, Lerma Edo. de
México 52000, México

The dynamic modeling and experimental validation of the model response of the poly(methyl methacrylate)
(PMMA) cell-cast process for plastic sheet production is presented. It is based on the straightforward initiation,
propagation, and termination reaction polymerization mechanism. The sheet molding process was modeled
by a two-dimensional dynamic mathematical model able to predict conversion, temperature, and molecular
weight averages. The mathematical model is cast as a partial differential equations (PDEs) system that is
discretized using the numerical method of lines. The resulting set of ordinary differential equations, representing
the heat and mass balances for this polymerization system, are then solved by standard ordinary differential
equations (ODE) solvers. Comparison of the model prediction capabilities against experimental temperature
measurements taken at the extremes of the PMMA sheet being produced are presented.

1. Introduction as are the largest windows and aquariums around the world.
The material is also used to produce laser disks, and sometimes
Global economy and high commercial pressure demand for DVDs. PMMA has a good degree of compatibility with
manufacturing better and cheaper products, reducing capital and human tissue and can be used for replacement of intraocular
operating costs. From a process systems engineering (PSE)1,2 lenses in the eye when the original lens has been removed in
point of view, there is a wide scope for process improvement the treatment of cataracts. In orthopedics, PMMA bone cement
by using advanced mathematical modeling techniques. Once a is used to affix implants and to remodel lost bone. Dentures
reliable model is available, it can be used for several purposes are often made of this material, too. Commercial production of
such as simulation, control, process synthesis, steady-state and PMMA sheets can be carried out by processes such as cell
dynamic process optimization, etc. Polymerization reaction casting (either in batch or continuous bulk polymerization), melt
engineering constitutes a field where process improvements can calendering, and melt-extrusion. The cell-casting process is
be achieved trough appropriate process modeling. A common becoming more important for PMMA production because of
disadvantage of polymerization products relates to product its flexibility in producing PMMA sheets with diverse physical
heterogeneous features due to variations in raw material quality, and mechanical properties.3
changing process operating conditions, etc. Product heteroge-
In Figure 1, one of the flowsheets for the industrial
neous characteristics tend to reduce process profit margins. By
manufacture of MMA is shown. In this, process monomer and
developing reliable polymerization models, process operating
small amounts of initiators react in a semibatch reaction system
conditions could be determined, leading to homogeneous product
where a prepolymerization step takes place. The aim of the
quality. Of course, the details embedded in a model will depend
prepolymerization step is to mix the reactants, to remove the
on its economical impact and the available process knowledge.
inhibitors normally contained in commercial MMA, and to heat
Working along the above ideas, in this work, our aim is to derive
the reaction mixture until polymerization reaction conditions
a first principles distributed dynamic mathematical model of
are reached. Normally, in the prepolymerization step, only
an industrial polymerization system and to validate it by
modest monomer conversion values (∼15-20%) are obtained.
comparing its dynamic response against experimental pilot-plant
The prepolymer material is introduced into the casting mold in
data. The reported work represents a long-term research effort
the form of a viscous liquid where polymerization reactions will
aiming to improve polymerization reaction operating conditions,
proceed until most of the remaining monomer is consumed. The
hence leading to better product characteristics and increased
polymerization of the material contained between the glass plates
profit margins, through advanced modeling, optimization, and
is then carried out by heating the molds while the glass plates
control techniques. In particular, in this work, we address the
are clamped together. Initially, when the reaction heat produced
poly(methyl methacrylate) (PMMA) industrial manufacturing
at low conversion is small (because of the very low polymer-
process.
ization rate at those conditions), heat is provided to the molds
PMMA is used, for instance, in the rear lights of cars. The
by inserting them inside hot water baths. There, PMMA plastic
spectator protection in ice hockey stadiums is made of PMMA,
sheet polymerization takes place. It has been reported4,5 that
this process tends to produce nonuniform (i.e., measured in terms
* To whom correspondence should be addressed. E-mail: of molecular weight averages) plastic sheets, because polym-
[Link]@[Link]. Phone/Fax: +52(55)59504074. http://
[Link]/∼antonio.
erization does not take place at the same rate inside the PMMA
†
Universidad Iberoamericana. polymerization mixture. Temperature variation is, perhaps, the
‡
Universidad Nacional Autónoma de México (UNAM) Conjunto E. main reason to explain polymer nonuniformity. Therefore, tight
§
Centro de Investigación y Desarrollo Tecnológico. control of the operating conditions should help to diminish the
10.1021/ie060206u CCC: $33.50 © 2006 American Chemical Society
Published on Web 09/28/2006
8540 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006

for PMMA plastic sheet manufacturing purposes. Similarly to

our work, Zhou et al.6 have reported a sheet-molding process
for the production of PMMA that involves a prepolymerization
batch reactor followed by polymerization in a sheet reactor.
However, they did not compare their results against experimental
data, and their formulation for heat energy balance considers
only unidirectional heat transfer. Moreover, the simulation
results presented by the authors do not reflect true operating
times, since their reported dynamic responses tend to be quite
faster when compared to characteristic industrial response times.
The authors showed temperature changes of ∼70 °C achieved
in only 30 s, while, according to our industrial experience, such
a response is achieved in ∼25 min.
Wanwanichai et al.7 report one- and two-step isothermal
sheet-casting processes for production of PMMA sheets with a
thickness of 3 mm, based primarily on water and water-air
systems. In the present work, we propose a dynamic two-
dimensional mathematical model able to reproduce the industrial
dynamic response of the cell-cast PMMA process. The dynamic
model is cast in terms of a two-dimensional partial differential
equation (PDE) system whose numerical solution was addressed
using the method of lines, giving rise to a system of ordinary
differential equations. The model considers free radical MMA
Figure 1. Traditional plastic sheet production flowsheet. bulk polymerization kinetics and heat conduction transport
within the polymerization mixture. The model response is vali-
dated against experimental pilot-plant data. Good agreement be-
tween model response and experimental plant data was observed.
We also present some simulation results for certain sheet plastic
widths for which experimental results were not available.

2. Modeling
2.1. Description of the System. Casting is the process
Figure 2. Cell-cast process for PMMA plastic sheet manufacture. whereby a liquid is poured into a mold and allowed to react,
cure, or harden to form a rigid object that takes the shape of
polymer nonhomogeneity problem. However, the above- the mold cavity. Many resin systems may be utilized in the
described traditional PMMA polymerization process using warm process, e.g., acrylic, diethylene glycol bis(allyl carbonate),
water baths features some shortcomings that could not be epoxy, phenol-formaldehyde, polystyrene, polysulfide, and
lowered by using even advanced control systems. Therefore, silicone. Methyl methacrylate is the principal monomer used
recently there has been interest in devising new and efficient in the casting, or bulk polymerization, process of acrylic plastics.
plastic sheet polymerization processes featuring homogeneous Acrylic sheets featuring high molecular weights are the primary
polymer properties. casting product; however, rods, tubes, spheres, lenses, and other
An interesting variation of the PMMA polymerization process intricate shapes may also be produced in batch casting. Plastic
described above consists of using a furnace like that shown in sheet is conventionally cast between two parallel heat resistance
Figure 2, where heat is provided by circulating warm air. There, glass plates, separated by a compressible gasket to allow for
the air temperature is modified by the cooling and heating shrinkage. The prepolymer material which may be mixed with
exchangers. During start-up, there is a radiator through which a mold release (stearic acid) is introduced into the casting mold
cooling water is circulating. There are many thin fins on the in the form of a viscous casting liquid. The polymerization
tubular surface, steam enters into the tubes, and the heat is between the glass plates is then carried out by subjecting the
exchanged to the air. Using the convective oven process for mold to heat while the glass plates are clamped together. The
plastic sheet production, PMMA polymer homogeneity features glass plates are stacked inside a so-called sheet reactor, as shown
could be more easily enforced. A warm air temperature profile in Figure 2. Depending upon the intended end use, plastic sheets
along the plastic sheet could be imposed and tracked by a control of different widths can be manufactured. As the width of the
system. In pilot-plant experiments, it has been found that plastic sheet rises, so does the polymerization time because of
convective ovens, when properly operated, increase the PMMA heat transfer resistance and viscous effects. It is well-known
polymer homogeneity characteristics and reduce the operating that careful control of the polymerization operating conditions
time allowed for complete polymerization. Moreover, temper- is necessary in order to obtain a bubble-free product of good
ature profile variations are faster to achieve when using air rather optical clarity. When the polymerization is about to begin, the
than water as the heating medium. This operating aspect charge molds are inserted inside a furnace which is heated by
becomes important if an on-line control system is used for circulating warm air, as displayed in Figure 2. Industrial
quality control. It could also be important for temperature profile experience has demonstrated that the best results are obtained
variations required to manufacture plastic sheets of widely if the plates are extended in a horizontal plane during polym-
different widths. erization so as to negate as much as possible the hydrostatic
In the research literature, there have been relatively few pressure of liquid monomer or prepolymer, which has a tendency
research papers dealing with the modeling of convective ovens to cause outward building of the glass plates. During the
 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006 8541

polymerization step, the temperature is maintained at such a

value that rapid polymerization takes place without, however,
permitting the temperature to run away so as to lose effective
control over the thermal conditions. If the temperature rises too
quickly, the polymerization may proceed like a chain reaction
resulting in undesirable characteristics of the final product.
Therefore, heating profiles may become an important manipu- Figure 3. Control volume for energy balance.
lated variable to enforce tight control on the polymer properties.
This issue will be deeply explored in future work and is one of 2.3. Kinetic Model. The two major problem sources encoun-
the reasons why we undertake the derivation, and experimental tered in industrial mass polymerization processes are the heat
validation, of a dynamic model able to mimic industrial cell- released by the highly exothermic reactions and the large
cast PMMA polymerization operating conditions. increase in viscosity of the reacting mixture over the course of
2.2. Process Mathematical Model. The cell-cast PMMA the polymerization. For a typical addition polymerization, the
mathematical model was derived assuming that the heating heat of polymerization ranges from 10 to 20 kcal/mol, which
source resulting from polymer reactions is a function of the local can result in an adiabatic temperature rise of ∼200-400 °C.
temperature. It was also assumed that polymer properties This large release of heat, coupled with the low thermal
changed along the length (x-axis) and width (y-axis) of the diffusivity of the reacting mixture, often leads to thermal
plastic sheet as depicted in Figure 3. For simplicity, the glass runaway conditions. Therefore, proper control of the process is
plates are considered homogeneous and isotropic, i.e., the difficult. A temperature rise generally lowers the degree of
properties are the same in all directions (thermal conductivity, polymerization. Hence, large temperature variations in the course
heat capacity, and density), and the average values were taken of the reaction broaden the polymer molecular weight average,
for MMA and PMMA. To derive the two-dimensional dynamic with accompanying deterioration of mechanical properties of
energy balance, the total heat entering and leaving at the x and the polymer. A quantitative cell-cast PMMA model able to
y coordinates was modeled by the Fourier heat conduction law, describe free-radical polymerization over the entire course of
and the rate of change of energy in the control volume was the reaction under both isothermal and nonisothermal conditions
obtained by applying the shell energy balance method.8 Because has not been fully established. It is especially desirable to
of symmetry considerations, only half of the sheet width (from develop such a mathematical model to predict the performance
the center to the external surface) was taken into account. From and outcome of the cell-cast PMMA polymerization process
a reaction engineering point of view, the PMMA plastic sheet and to correlate the product specifications with various operating
process can be considered as taking place in a constant-volume parameters such as reactor temperature trajectory, initiator
batch reactor. Dynamic mass and energy balances coupled loading, etc.
through polymerization kinetics9 describe polymer conversion
The reaction mechanism adopted here consists of the well-
and molecular weights dynamic time evolution. Air is circulated
known free-radical polymerization kinetics featuring straight-
through the oven to provide the required energy to rise up the
forward initiation, propagation, and termination reactions. Chain-
plastic sheet temperature until a point where significant polym-
erization rates take place. We assume that heat is transported transfer reactions are neglected for convenience. The PMMA
by the forced convection mechanism. Inside the monomer, the free-radical polymerization model taking place in a batch reactor
dominant heat transfer mechanism is conduction. Therefore, heat is available elsewhere.9 However, we should mention that there
is transferred along the x and y axes, giving rise to the following are more complete kinetics polymerization models proposed in
two-dimensional dynamic heat transfer equation. the literature.10 For instance, good reviews on this topic have
been published by O’Neil et al.11 and Dubé et al.12 Although
∂T
∂t (
∂2T ∂2T
)R 2+ 2 +
∂x ∂y F
Q
MCp,M
) (1)
Vivaldo-Lima et al.13 have compared the effectiveness of the
Chiu et al.9 and Marten and Hamielec14 models, we found that
the model proposed in ref 9 is simple enough and able to repro-
which is subject to the following initial and boundary conditions duce PMMA polymerization characteristics. Therefore, in this
work, we use the polymerization kinetics and gel effect models
t)0 T ) T0 (2) as proposed by Chiu et al.9 The model is given as follows

∂T dI ǫI
x)0 -kM ) ha(T - Ta) (3) ) -kdI - λ k (1 - X) (7)
∂x dt 1 + ǫX 0 p
∂T dX
x)L )0 (4) ) λ0kp(1 - X) (8)
∂x dt
∂T
y)0 )0 (5) dλ0 ǫλ02
∂y )- (1 - X)kp + 2fkdI - ktλ02 (9)
dt 1 + ǫX
∂T
y)H -kM ) ha(T - Ta) (6) dλ1 ǫλ1λ0
∂y )- (1 - X)kp + 2fkdI - ktλ0λ1
dt 1 + ǫX
where T is the polymer temperature, T0 is the initial monomer 1-X
temperature, Ta is the surrounding temperature, L is the sheet + kpλ0M0 (10)
dλ2 ǫλ2λ0 1 + ǫX
length, H is the sheet thickness, k is the average thermal )- k (1 - X) + 2fkdI - ktλ0λ2 +
conductivity, F is the density, Cp is the heat capacity, R is the dt 1 + ǫX p
thermal diffusivity, ha is the heat transfer coefficient, and Q 1-X
kpM0 (2λ + λ0) (11)
stands for the heat released by the polymerization reactions. 1 + ǫX 1
8542 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006

dµ0 ǫµ0λ0 1
)- k (1 - X) + ktdλ02 + ktcλ02 (12)
dt 1 + ǫX p 2
dµ1 ǫµ1λ0
)- k (1 - X) + ktdλ0λ1 + ktcλ0λ1 (13)
dt 1 + ǫX p
dµ2 ǫµ2λ0
)- k (1 - X) + ktdλ0λ2 + ktc(λ2λ0 + λ12) (14)
dt 1 + ǫX p
where ǫ represents the volume expansion factor determined by

(Fm - Fp) Figure 4. Notation used to identify grid points.

ǫ) (15)
Fp Table 1. Simulation Data for Batch Reactor
initial monomer & initiator conc. 9.98 & 0.0258 mol/dm3
Molecular weight averages were calculated from the moments initial monomer conversion X)0
method15 as follows, initial living & dead moments λ 0 ) 0 & µ0 ) 0 mol/dm3
polymer density 1200 kg/m3

( ) ( )
µ1 + λ 1 m µ2 + λ 2 m initial temperature 343.15 K
Mn ) Mw , Mw ) M (16) initiator efficiency 0.58
µ0 + λ 0 µ1 + λ1 w
Table 2. Simulation Data for Sheet Reactora
where λ0, λ1, and λ2 are the zeroth and first moments of the monomer & initiator initial conc. Mout-batch & Iout-batch mol/dm3
growing radicals; µ0, µ1, and µ2 are the zeroth, first, and second monomer conversion Xout-batch
living & dead moments λ0out-batch & µ0out-batch mol/dm3
moments for the dead polymer, respectively; and Mm w is the heat of reaction -58.19 kJ/mol
monomer molecular weight. polymer thermal conductivity 0.09 W/(m-K)
The above set of equations are subject to the following initial polymer heat capacity 1674 J/(kg-K)
conditions: air temperature 318 K
initial temperature 298.15 K
sheet length 1.8 m
I ) I0, X ) X0, λ0 ) λ00 ,λ1 ) λ10, λ2 ) λ20, sheet thickness 0.003, 0.006, 0.012, m
µ0 ) µ00, µ1 ) µ10, µ2 ) µ20 (17) & 0.018
a The subscript out-batch means that the numerical value of the property

2.4. Model Solution. The application of the method of lines16 is taken as the one at the outlet of the batch reactor.
is an alternate approach for solving the set of partial differential
equations describing the PMMA cell-cast process. We use this where ∆x ) L/(Nx - 1) and ∆y ) H/(Ny - 1). Here, we have
method for addressing the spatial discretization of both the PDE, used the well-known second-order finite difference approxima-
which models temperature variations along the plastic sheet, as tion for the first and second derivatives along the x- and y-axes.
given by eq 1, and the boundary conditions (eq 2). The The backward difference formula was applied to the boundary
discretized equations thus obtained form a set of differential- conditions at x ) 0 and y ) 0, and the forward difference
algebraic equations which can be numerically integrated by formula was used at x ) L and y ) H. In the definition of the
standard integration routines17 as an initial value problem. When finite differences, the point of reference is taken to be the point
the left-hand side of eq 1 is approximated by the method of Tij in Figure 4. After some trials, we found that 20 and 8 points
lines, one obtains suffice to represent the system dynamic response along the

( )
longitude and thickness of the plastic sheet, respectively.
dTij Ti-1j - 2Tij + Ti+1j Tij-1 - 2Tij + Tij+1
)R + +
dt ∆x2 ∆y2 3. Results
Qij The aim of this section is to validate the response of the
, i ) 2, ..., Nx - 1, j ) 2, ..., Ny - 1 (18)
FMCp,M underlying cell-cast PMMA mathematical model by comparing
it against industrial pilot-plant experiments. To this end, several
similarly, the boundary and initial conditions are transformed experiments were run at a local pilot-plant facility using plastic
as follows sheet thicknesses of 3 and 6 mm. Because of technical
difficulties for carrying experiments using a larger sheet
3T1j - 4T2j + T3j thickness, only open-loop simulation results are presented for
kM ) ha(T1j - Ta) (19) 12 and 18 mm plastic sheet thicknesses. Even when a direct
2∆x
experimental comparison was not carried out, good qualitative
3TNxj - 4TNx-1j + TNx-2j agreement was also observed. Moreover, it is hoped that the
)0 (20) predictive capabilities of the model would allow us to extrapolate
2∆x
its response for larger thicknesses. In Table 1, design data for
-3Ti1 + 4Ti2 - Ti3 the prepolymerization step carried out in a batch reactor are
)0 (21)
2∆y shown, while Table 2 contains the corresponding design data
for the PMMA plastic sheet reactor. Information regarding the
3TiNy - 4TiNy-1 + TiNy-2 PMMA kinetic rate constants is displayed in Table 3.
kM ) ha(TiNy - Ta) (22)
2∆y Pilot-plant experiments were conducted under isothermal
conditions; during all the experiments, air was forced to be
t ) 0 Tij ) T0 i ) 1, ..., Nx, j ) 1, ..., Ny (23) circulated and kept at 50 °C. To record sheet temperatures, two
 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006 8543

Figure 5. Comparison of experimental (o) versus simulation results. The continuous line stands for constant physical properties, while the short dashed line
(- - -) represents results obtained allowing temperature-dependent physical properties and the large dashed line (- -) represents dependent conversion besides
temperature. (a) and (b) are temperature results for 3 mm sheet thickness at x ) 0 and x ) L, while similarly, (c) and (d) represent temperature results for
a 6 mm sheet thickness at x ) 0 and x ) L.

Table 3. PMMA Kinetic Rate Constants

apparent propagation coefficient9

1
)
1
kp kp0(T)
+ θp(T)λ0 exp -( 2.3φm
A + B(T)φm )
apparent termination coefficient9
1
)
1
kt kt0(T)
+ θt(T, I0)λ0 exp -( 2.3φm
A + B(T)φm )
14 000
monomer diffusion time for propagation stage9 (
θp ) exp -35.167 +
T )
17 500
θ ) exp(-46.983 +
T )
monomer diffusion time for termination stage9 t

parameter A in the Fujita-Doolittle equation21 A ) -8 × 10-6(T - Tg)2 + 0.1678

parameter B9 B ) 0.03
4353
true propagation coefficient9 (
kp0 ) 2.95 × 107 exp -
1.987T )
701
true termination coefficient9 (
kt0 ) 5.88 × 109 exp -
1.987T )
14 855
initiator coefficient22 (
kd ) 4.25 × 1016 exp -
T )
1-X
volume fraction of the monomer9 φm )
1 + ǫX
kinetic coefficient for termination kt ) ktc + ktd
kinetic coefficient for termination by addition9 ktc ) 0
glass transition temperature Tg ) 387.15

termocouples were located at the x extremes (x ) 0 and x ) L) ported; no measurements related to the prepolymerization stage
of the sheet. A data acquisition system was used for on-line were recorded. As depicted in Figure 5a, because of the warm
temperature recording using sampling intervals of 7 min. Only air flow direction, at x ) 0 the temperature rises quicker when
polymerization temperatures recorded at the furnace are re- compared to the same temperature increase at x ) L, as
8544 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006

Figure 6. Temperature dynamic profiles for (i) 3, (ii) 6, (iii) 12, and (iv) 18 mm at (a) y ) 0 (interior middle point) and (b) y ) H (external plate surface).
Solutions are labeled for the edge (x ) 0) and right extreme (x ) L) along the longitudinal x-coordinate. The rest of the nonlabeled temperature profiles
correspond to discretized points along the x-coordinate.

displayed in Figure 5b. After 4 h, the sheet temperatures properties (i.e., conversion, molecular weight averages, etc.)
acquired the steady-state value. Here, steady state means that, remain constant. However, at x ) L, the temperature dynamic
after the reaction has been essentially completed, polymer response is slower, but finally it also attains the steady-state
 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006 8545

Figure 7. Monomer conversion profile along the longitude of the plastic sheet: s, x ) 0; - -, x ) L/4; - ‚ -, x ) L/2; and ‚ ‚ ‚, x ) L for (a) 3 mm,
(b) 6 mm, (c) 12 mm, and (d) 18 mm plastic sheet thickness.

Table 4. Temperature- and Conversion-Dependent Properties

Fm (0.973 - 1.164 × 10-3(T - 273)) × 1000
km 0.13
Cpm 1.674
Fp (1.9872 - 3.971 03 × 10-3T + 4.4626 × 10-6T2) × 1000
kp -0.06852 + 8 × 10-4T
Cpp 1.45
FM FpX + Fm(1 - X)
kM kpX + km(1 - X)
Cp,M Cp,pX + Cp,m(1 - X)
ka 2 × 10-8T2 + 7 × 10-5T + 0.0243
νa 13.638 e(0.0052T)x10-6
Pra -7 × 10-7T2 - 5 × 10-5T + 0.7145
Rea LV/νa
ha 0.0288Rea4/5Pra1/3ka/L

value when the polymerization reaction has been completed. In all the simulation responses discussed so far, constant
In both figures, a temperature peak can be clearly seen. The physical properties were assumed. In a real industrial environ-
peak is related to the onset of the gel effect, and it is larger at ment, it is unlikely that such an assumption can be justified.
x ) L because, at this point, thermal effects are stronger because Commonly, constant physical properties are assumed because
of the heat produced by the reaction contribution. At x ) 0, the this assumption can drastically lower the computational load
simulation and experimental results are shifted by 15 min. needed for model solution. However, with the advent of power
Moreover, at x ) L, the agreement between simulation and computer processors and/or parallel computing environments,
experimental results is good. assumptions such as the one discussed above can be relaxed,
8546 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006

Figure 8. Initiator concentration profile along the longitude of the plastic sheet: s, x ) 0; - -, x ) L/4; - ‚ -, x ) L/2; and ‚ ‚ ‚, x ) L for (a) 3 mm,
(b) 6 mm, (c) 12 mm, and (d) 18 mm plastic sheet thickness.

leading to models with improved prediction capabilities. To get relatively modest computational loads for getting the same type
a clear idea about modeling improvements, physical properties of model response.
were made a function of temperature, using the physical In parts c and d of Figure 5, temperature dynamic responses
properties correlations as displayed in Table 4. Moreover, some for a 6 mm plastic sheet thickness are shown. The experimental
properties were also assumed to be a function of monomer temperature response becomes slightly sluggish when compared
conversion (X). In Figure 5, the temperature dynamic response to the similar 3 mm plastic sheet temperature response. As the
using temperature-dependent physical properties is displayed sheet thickness increases, so do the heat transfer limitations;
by dashed lines. For the 3 mm plastic sheet thickness, the this explains the rise in the process time constant. It is also
predicted results using either constant or temperature-dependent interesting to realize the growth of the temperature peak: as
physical properties look similar. The CPU time on a Pentium 4 the sheet thickness increases, so does the temperature peak. This
PC computer running at 2.6 GHz for the physical properties as behavior can be partially attributed to the availability of larger
a function of temperature was ∼320 min, while for the constant- amounts of monomer that contribute to extend the gel effect
temperature case, it required only 11 min. Intuitively, because outcome. Moreover, this behavior is related to the lower mass/
of heat transfer limitations leading to large local temperature heat transfer area ratio. Hence, heat accumulation occurs as a
spots, we expect that good model prediction capabilities for a consequence of greater amounts of released heat. Another point
larger sheet thickness will require temperature-dependent physi- to highlight is that, regardless of the sheet thickness, the
cal properties. As seen from Figure 5, if the physical properties temperature peak occurs at practically the same operating time.
are both temperature- and conversion-dependent, the predicted Overall, the predicted temperature response is not as good as it
results are better than the cases of only temperature-dependent was for the 3 mm sheet thickness; even using temperature-
physical properties. However, because physical properties as a dependent physical properties, the model response could not
function of conversion and temperature require quite large CPU be further enhanced. We decided to use the same numerical
computer times (∼48 h) to get a typical model response, we values of the physical and kinetic constants in both the 3 and 6
will keep using constant physical properties that demand mm sheet thicknesses. This partially explains the worsening in
 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006 8547

Figure 9. Number-average molecular weight profile along the longitude of the plastic sheet: s, x ) 0; - -, x ) L/4; - ‚ -, x ) L/2; and ‚ ‚ ‚, x ) L for
(a) 3 mm, (b) 6 mm, (c) 12 mm, and (d) 18 mm plastic sheet thickness.

temperature response. Although some model improvement could profiles are larger than the external ones because of the cooling
be achieved by proper parameter fitting, we decided not to do effect of air flowing over the plastic sheet. Moreover, as the
so to test the validity of our model using standard physical and polymerization reaction goes on, polymer viscosity increases,
kinetic parameter values. Of course, real time use of the model leading to heat transfer limitations. Hence, heat dissipation
would require additional off-line and perhaps on-line parameter becomes harder to achieve. In Figure 6, we also note that the
estimation. gel effect suddenly appears at different times for a long plate;
Figure 6 displays plastic sheet temperature profiles at y ) 0 this autoacceleration effect causes a conversion rate increment,
(interior middle point of the plate) and y ) H (surface of the driving the system (see Figure 7c) from 0.85 to 0.94 conversion
plate) along the longitude of the sheet corresponding to the degree. This effect suffices to obtain a nonuniform plate
x-coordinate as shown in Figure 3. The results depicted in Figure thickness (see Figure 12c). In this case, there is a thickness
6 were obtained by solving the cell-cast PMMA dynamic two- difference of ∼0.2 mm (1.6%) between the plastic sheet edges.
dimensional model given by eqs 1-17, and corresponding to The initial edge (x ) 0) of the sheet reactor is closest to the
3, 6, 12, and 18 mm plastic sheet thicknesses. Temperature heat source (the air flow rate). In consequence, the temperature
profiles are labeled for the edge (x ) 0) and end (x ) L) parts rise in this zone is higher than in the rest of the sheet. This is
of the sheet; the rest of the nonlabeled temperature profiles the reason the onset of gel effect appears first there rather than
correspond to intermediate longitudinal points. As can be seen, in the rest of the system. Because the initial edge of the sheet
the shape of the temperature profile is very similar for the 3 is the one with the quickest temperature response, it is also the
mm sheet thickness. Although the temperature profile shape one with the highest amount of instantaneous heat release
looks similar, the difference of the maximum peak temperature because of the exothermic nature of the MMA polymerization
tends to rise as sheet thickness is increased. Therefore, the reaction; the latter phenomenon clearly contributes to an even
internal temperature profiles (y ) 0) tend to be higher than the higher temperature rise. Even though the presence of this
external ones (y ) H). Indeed, for the 18 mm sheet thickness, temperature sudden rise, due to the onset of the autoacceleration
the temperature difference is ∼6 °C. Internal temperature effect, can act like the driving force for heat transfer to the rest
8548 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006

Figure 10. Weight-average molecular weight profile along the longitude of the plastic sheet: s, x ) 0; - -, x ) L/4; - ‚ -, x ) L/2; and ‚ ‚ ‚, x ) L for
(a) 3 mm, (b) 6 mm, (c) 12 mm, and (d) 18 mm plastic sheet thickness.

of the sheet reactor, the heat transfer resistance in the internal terminated by interpolymeric reactions in which pairs of living
part of the sheet is higher than the one presented by the glass chains annihilate each other. Each termination reaction results
at the interface. Hence, most of the heat flow is exchanged at in a dead chain; this is the final polymer product. In Figure 7,
the interface by convection with the flowing air. Figure 6 shows we see that monomer conversion gradually increases with the
the final temperature profile once monomer has been almost polymerization temperature. Note that monomer conversion is
totally consumed, as can be seen at Figure 7, too. At this time, lowest at 50 °C; this is consistent with the glass effect, whereby
the polymerization reaction in the sheet reactor is over and the the reaction mixture essentially freezes at a concentration whose
amount of heat generated by the reaction has been totally glass transition temperature (Tg) corresponds to the reaction
exchanged with the air, so the system attains thermal equilibrium temperature. Another important feature characterizing both the
conditions. Because of the initial and operating conditions of experimental temperature data and the predicted curves is the
the system, final values of ∼0.9 conversion were obtained. A curvature of the conversion profile before the onset of the so-
widely used technique in the polymerization industry is the called gel region. The monomer conversion profile is homo-
postcuring stage of the sheet (see Figure 1), well above the glass geneous (meaning that the conversion profile is almost the same
transition temperature of the polymer, to consume the remaining at any point on the plastic sheet) along the 3 mm thickness flat
monomer. plate, as shown in Figure 7a, while the same conversion profile
The basic chemistry involved in free radical polymerization is slightly heterogeneous for the 6 mm thickness plastic sheet,
is by now well-established.18 Highly reactive free radical species as seen in Figure 7b. These curves are convex form preceding
trigger fast chain reactions, adding monomers into polymer the sharp rise. When the gel effect appears suddenly, the
chains as follows. When a free radical attacks a monomer, it movements of polymer chains are restricted as a result of the
transfers its active center to the monomer itself, initiating a live high viscosity of the reaction mixture; this leads to a dramatic
growing chain, or macroradical, as successive monomers are decrease in the termination rate constant and significant auto-
added in similar fashion. These living chains propagate into the acceleration of the polymerization because of the increased free-
surrounding monomer medium, with their growing ultimately radical concentration. Thus, at extremely high conversions, even
 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006 8549

Figure 11. Polydispersity profile along sheet longitude: s, x ) 0; - -, x ) L/4; - ‚ -, x ) L/2; and ‚ ‚ ‚, x ) L for (a) 3 mm, (b) 6 mm, (c) 12 mm, and
(d) 18 mm plastic sheet thickness.

the movements of small molecules are restricted, lowering the affected by the thickness of the sheet. For sheet adjacent points,
propagation rate constant and possibly leading to a complete the spectacular decrease in initiator concentration is accompa-
termination of polymerization. Therefore, the portion of the nied by rapid temperature rises; this is a consequence of the
conversion curve under examination would be concave. Hence, autoacceleration effect. Also, increasing temperature at a
a major difference exists between the present model and other constant initiator loading significantly lowers the molecular
contemporary ones in that our model incorporates diffusion in weight. At high conversions, when termination rate is greatly
the basic sequence of events constituting the termination of reduced, the average molecular weight rises appreciably.
growing radicals from the very outset of reaction. Onset of gel The influence of the process variables on the characteristics
effect is only a convenient phrase denoting the region of rapid of the product can be understood from the molecular weight
increase in monomer conversion. There exists, in fact, no sharp average (Mw) profiles calculated by the method of moments. It
demarcation in terms of molecular processes before and after is well-known that the material properties (stress-strain, tough-
the occurrence of this autoacceleration region. The rapid rise ness, and fracture and fatigue behavior) depend on the molecular
in conversion is merely a natural consequence of the in- weight average of a given polymer.19 It has been reported that
creasing importance of mass transfer limitations.9 Figure 7 mechanical properties improve with molecular weight up to a
clearly displays a critical problem arising in the isothermal cell- number average ∼105. The molecular weight averages for a long
cast process: as the plastic sheet thickness rises, so do the flat plate are plotted in Figure 10 for 3 and 6 mm plastic sheet
heterogeneous characteristics of the plastic sheet, leading to thicknesses. The effect of a runaway scenario on the molecular
sheet zones of different polymer properties (i.e., conversion, weight is associated with the gel effect. It can be seen that Mw
molecular weight average, etc.). Heterogeneity could be low- decreases along the plastic sheet from 3% to 6% as seen in
ered, to a certain extent, by manipulating the air flow rate Figure 10a, in agreement with basic rules-of-thumb,20 meaning
temperature. that the net effect of temperature rise is a decrease in the
In Figure 8, the dynamic evolution of the initiator concentra- molecular weight profile. On Figure 10b, the Mw profile
tion is shown. It can be seen that the initiator concentration decreases compared to the 3 mm plate; Mw falls from 4% and
decreases linearly at the initial edge of the sheet, and it is not 11% for the middle and final points, respectively. Similar
8550 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006

Figure 12. Variation of plastic sheet thickness: s, x ) 0; - -, x ) L/4; - ‚ -, x ) L/2; and ‚ ‚ ‚, x ) L for (a) 3 mm, (b) 6 mm, (c) 12 mm, and (d) 18
mm plastic sheet thickness.

behavior is observed for large plastic sheet thicknesses, as of a second population of chains of different molecular weights
depicted in Figure 10 parts c and d. is responsible for the drastic increase in the polydispersity index
On Figure 11, the polydispersity index is displayed at four after the highest plastic sheet temperature is reached.
points along the longitude of the plastic sheet. Since the In Figure 12, thickness variation behavior for the four cases
polydispersity index measures the breadth of molecular weight explained above is displayed. The first case, Figure 12a, has a
average, it is expected to increase when the instantaneous uniform shrinkage and features an estimated 18% thickness
molecular weight undergoes large variations during the course variation between the initial and end time for the polymer
of the reaction. In parts c and d of Figure 11, we can see that reaction. In Figure 12b, the plastic sheet has an 18% thickness
the dotted line (x ) L) corresponds to the one showing the variation and 0.7% variation (not shown) along the sheet
highest temperature peak, as depicted in Figure 6. Therefore, longitude; this last change is not really important. Thickness
gel effect onset and dramatically runaway conditions seem to variation problems do not decrease as polymer sheet width rises.
be accompanied by substantial increases in the polydispersity Indeed, as displayed in parts c and d of Figure 12, plastic sheets
index. When the peak of maximum temperature is reached, the of 12 and 18 mm also feature ∼18% thickness variation. Wide
polydispersity index abruptly levels off, since the reaction is thickness variation is a severe problem that could be lowered
prematurely stopped by the depletion of initiator, as displayed by proper process operation. We could achieve homogeneous
by dotted lines in Figure 8 parts c and d. The plastic sheet zones thickness by eliminating the high-temperature behavior at the
featuring temperature peaks can have a disastrous consequence end edge for both cases. If the heating profile is near to
on the polydispersity index. As shown by the conversion profiles isothermal conditions, uniform shrinkage during the cell-cast
corresponding to these cases, a significant amount of polymer process will be promoted.
is still formed beyond the hot spot. The chains formed after a Figure 13 depicts the variation of temperature and monomer
runaway situation, however, have a different molecular weight, conversion profiles at quarter (x ) L/4) and half (x ) L/2) the
since many process variables and characteristics of the polymer- plastic sheet longitude for three points along the y-coordinate:
izing medium (initiator concentration, temperature, and, con- the center (y ) 0), the surface (y ) H), and half of the thickness
sequently, termination rate kinetics) have changed. The growing (y ) H/2). In Figure 13a, the temperature rises slowly and the
 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006 8551

Figure 13. Predicted temperatures and monomer conversion: s, y ) 0; ‚ ‚ ‚, y ) H/2; and - ‚ -, y ) H for (a) and (b) x ) L/4, and (c) and (d) x ) L/2
for an 18 mm thickness plastic sheet.

temperature of the surface is greater than the one at the center, gets 88% and 90% values at the central and surface points,
because the air heats the surface of the sheet, and heat is respectively.
transported into the bulk polymerization through the heat Even when, in this work, no parameter estimation was
conduction mechanism. At ∼300 min, the gel effect appears undertaken, a parameter sensitivity analysis was carried out.
and the difference of temperature change becomes maximal, 4 Model response was sought for small changes on the free
°C at 300 min. After that, the temperature approach, T(y ) 0) volume parameters (A, B, θp, and θt). Chiu et al.9 report that A
- T(y ) H), is zero at 500 min and the temperature is 71.5 °C. increases with the temperature, and its range of change is small
From this time on, the inner temperature will be greater than (0.13-0.16) on the temperature operation range. However, there
the surface temperature; thus, the heat produced by the reaction was not an effect on changing this parameter for the model
is not removed efficiently by the air. The plastic sheet thermal response. It has been found empirically that B is not sensitive
behavior affects the monomer conversion. Indeed, we can see to temperature for many systems and can be treated as a
in Figure 13b that, for the first 300 min, the conversion is almost constant. θp and θt reflect primarily the behavior of the diffusion
35%, but suddenly, it becomes too high, 82% and 85% at the coefficient at the limit of vanishing the volume fraction of the
inner and surface plate positions, respectively. When the monomer for termination and propagation, respectively, and θt
temperature approach is zero, the monomer conversion is 91%; is a function of initial initiator concentration, too. Small changes
this is near to maximum conversion for final polymer processing. on θp did not not significantly affect model response. We found
It should be noticed that the thermal response at half and quarter that θt mainly affects sheets featuring a larger thickness, because
plate is very similar, but now in Figure 13c, the temperature this parameter reflects the mass transport processes for growing
approach becomes too large, 24 °C at 400 min, and so forth; radicals and monomer. Figure 14 displays the temperature
the cross-temperature appears at 435 min and its temperature behavior when θt is (5% changed. In parts c and d of Figure
value is 90 °C, greater than the case of quarter plate. In Figure 14, the sensitivity results are shown for 6 mm sheet thickness
13d, the monomer conversion increases slowly from 0 to 350 at x ) 0 and x ) L, respectively. If we change θt by -5%, it
min, but when the gel effect appears, it grows suddenly and was found that the simulation results display a better matching,
8552 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006

Figure 14. Comparison of experimental (o) versus sensitivity simulation results: (s) physical constant properties, (‚‚‚) physical dependent properties (for
the same θt values), (- ‚ -) when θt is affected on changing by -5%, and (- -) when θt is affected on changing by +5%. (a) and (b) are temperature
results for 3 mm sheet thickness at x ) 0 and x ) L, respectively, and (c) and (d) represent temperature results for 6 mm sheet thickness at x ) 0 and x )
L, respectively.

because the diffusional effect increases and then the temperature temperature trajectories able to maintain uniform molecular
increases faster, showing a larger peak. weight averages to achieve the specified product quality. Once
the optimal temperatures profiles have been computed, the
4. Conclusions problem of how to closed-loop track such optimal transition
trajectories, in the presence of modeling errors, remains.
Good agreement between pilot-plant experimental results and
model predictions for the cell-cast PMMA plastic sheet process Nomenclature
was confirmed. A dynamic two-dimensional model able to
predict conversion rate, molecular weight, and temperature Cp ) heat capacity (J/kg‚K)
distributions in a PMMA cell-cast sheet reactor was developed. f ) initiator efficiency
From the results discussed in this work, we can conclude that h ) heat transfer coefficient [W/(m2 K)]
the proposed model is a useful tool to test the advantages of H ) sheet thickness (m)
using heating ovens for the sheet polymerization process. In I ) molar concentration of initiator (mol/dm3)
contrast, the traditional PMMA polymerization process using k ) thermal conductivity [W/(m‚K)]
warm water baths tends to produce both nonuniform conversion kd ) kinetic coefficient for initiator (1/min)
rates and molecular weight averages. Therefore, by proper ki ) kinetic coefficient for initiation reaction [dm3/(min‚mol)]
operation, heating ovens should lead to obtaining polymerization kp ) kinetic coefficient for propagation [dm3/(min‚mol)]
products with uniform polymerization properties. Comparison ktc ) kinetic coefficient for termination by addition [dm3/(min‚
against experimental data shows that the model prediction mol)]
capabilities seem to be satisfactory for industrial application. ktd ) kinetic coefficient for termination disproportionation [dm3/
Hence, we expect to use this model to compute optimal (min‚mol)]
 Ind. Eng. Chem. Res., Vol. 45, No. 25, 2006 8553

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