Chemical Engilwering Science, Vol. 40, No. I, pp. 75-86, 1985. 0009 -2509/85 :!i3.

oo + o_oo
Printed in Great Britain. Pergamon Press Ltd.

MAJOR FACTORS CONTRIBUTING TO THE

NONLINEAR KINETICS OF FREE-RADICAL
POLYMERIZATION

P. E. BAILLAGOU and D. S. SOONG t

Department of Chemical Engineering, University of California, Berkeley, CA 94720, U.S.A.

(Received 16 January 1984)

A�tract-Predictions based on a recently developed model for nonisothermal free-radical polymerization

with ge� e ��t are made for batch and plug-flow systems. The often observed nonlinear kinetic phenomena,
such as 1gmt1on, thermal runaway, dead ending and autoacceleration are clearly separated into parametrically
dependent and gel effect induced categories. This analysis identifies major causes for the difficulties
encountered in polymerization reaction engineering and serves as the basis for future modeling of realistic
processes, where the fluid mechanics also plays an important role in governing reactor performance and
product quality.

INTRODUCTION weight distribution (Martin et al., 1972; Nunes et al.,

The conversion of monomer into polymer reduces the 1982). In general, mechanical properties are improved
free volume of the reaction mixture. This results in a by low polydispersity and high molecular weights. The
great increase of the viscosity of the polymerizing typical goal is to maintain polydispersity to as low as
medium; mixing and pumping problems can occur possible arrd to achieve a minimum molecular weight

even at low conversions ( - 30 %). When the reactor is in the neighbourhood of 105• Since the product quality
operated below the glass transition temperature of the is determined by the processing history experienced by
polymer, total conversion cannot be achieved because the reaction fluid, gel effect and thermal run-away must
monomer diffusion to reacting radicals is seriously generally be avoided. Sacks et al. ( 1973) have de­
hampered by the high viscosity of the reaction mixture. termined the optimal temperature history in a batch
A related consequence of the decrease in the free reactor and shown that product quality is indeed

volume is the gel effect (Trommsdorff et al., 1947), intimately related to the control of the reactor.
which causes autoacceleration of the overall rate of The use of tubular reactors is inherently an attract­
polymerization, observed even under isothermal con­ ive alternative for the mass production of high quality
ditions. This phenomenon, particularly strong in the polymers. Continuous operation allows high through­
case of MMA polymerization, will be a focus of this puts at a low cost. This reactor is distributed; the

work. governing space variable can be used for process

Polymerization reactions are highly exothermic optimization, similar to the use of temperature history
(releasing 10-20 kcal/g mol). Unfortunately, mono­ in a batch reactor to generate desirable polymers.
mer-polymer solutions have small thermal diffusivities Hence, in principle a tubular reactor would combine
and low heat capacities. Convective heat transfer is the advantages of both a CSTR (continuous) and a
retarded by the high viscosity of the fluid, which batch reactor (optimizable). However, in practice
decreases mixing efficiency. This unfavourable combi­ stirred tanks are easier to control and have better
nation of the thermodynamics of the reaction and the mixing characteristics than tubular reactors. Mixing
physical properties of the reactive mixture makes and heat transfer efficiencies in tubular reactors are
reaction temperature very difficult to control. Thermal generally not sufficient to overcome process difficulties
run-aways often ensue. We will thus devote much accompanying polymerization. Furthermore, the vel­
attention to this phenomenon in the present study as ocity profile in a real tubular reactor is far from that of
well. a plug-flow reactor. A longer residence time and
Despite the difficulties confronting polymerization therefore higher conversion is to be expected near the
reaction engineers, the use of polymers as structural wall. Consequently, a very high viscosity gradient
materials often generates stringent performance re­ develops along the radius of the tube, which in turn
quirements of a polymerization process, e.g. steady aggravates the already nonlinear velocity profile. This
production rates and reproducible mechanical pro­ distorted velocity profile eventually leads to the forma­
perties of the product. Steady throughputs are realized tion of a thick stagnant layer of polymer, which slowly
more easily and at lower costs b y continuous processes. coats the wall and reduces the capacity of the reactor
The important mechanical properties of a polymer (Lynn and Huff, 1971).
have been shown to depend strongly on the molecular Most publications in the polymerization reaction
engineering literature address only parts of the above
problems. The gel effect was experimentally studied
t Author to whom correspondence should be addressed. and the results modeled, but only for isothermal

75
76 P. E. BAILLAGOU and D. s. SoONG

conditions. On the other hand, non-isothermal be­ First, a r�listic gel effect model has been developed to
haviour was investigated, but the gel effect was neglec­ describe the polymerization of methylmethacrylate
ted in the analysis. The kinetic models developed to over the entire course of reaction (Chiu et al., 1983).
date have been extensively used to predict molecular This model is here used for the simulation of non­
weight averages. However, attempts to correlate the isothermal reactions in plug-ft.ow reactors. At this level
entire molecular weight distribution with reaction of approximation, the rheology is decoupled from
conditions have seldom been made. Incomplete mathe­ kinetic considerations. Autoacceleration, ignition and
matical models are also often found in tubular reactor thermal run-away phenomena can be traced distinctly
literature. Some papers emphasi.z.e the kinetics but to separate causes by simple kinetics analyses. Next,
ignore the transport problem by assuming plug-ft.ow. the complete kinetic model is employed together with a
The opposite has also been reported, i.e. extensive realistic viscosity constitutive relation for accurate
study of the velocity profile with a poor kinetic model. descriptions of the velocity, conversion and tempera­
Most previous works on tubular polymerizers focus on ture profiles in tubular reactors. The predictions of this
the polymerization of styrene. This system is not model are compared with the plug-flow simulations.
representative of all the polymerization difficulties, Experiments have been conducted to verify model
because it exhibits only a very weak gel effect. In predictions and to pin-point the causes of problems
contrast, our project concentrates on the polymeriz­ often encountered in tubular polymerization pro­
ation of methyl methacrylate, whose gel effect is much cesses. Finally, a new operating strategy, polymeriz­
more severe. The polymerization of methyl meth­ ation at elevated pressures and above Tg temperatures,
acrylate poses particularly challenging problems in our is explored. The results of such experiments will be
studies. disclosed. The above segments of this ongoing research
The present program is divided into several phases. program will be published in a series of papers. This

Table I. Proposed free-radical polymerization mechanism

kd R"
I 2
Initiation
k.
1.
R + M P
i

kp
p.; + M p� + 1
Propagation

kt:m
p� + M Dn + Pi Chain transfer to monomer

kts
P,; + s
Dn+ Pi Chai.n transfer to solvent

kt:d
p,; + Pm Dn+Dm Termination by disproportionation

ktc
p� + Pm 0n+m Termination by combination

where

I Initiator

R Primary radical

M Monomer molecule

S Solvent molecule

P� Macroradical of length n

00 Dead polymer of length n

 Free-radiail polymerization 77

paper only addresses issues concerning the major non­ perature rise, making run-away a likely event during
isothermal and nonlinear features of polymerization polymerization. Biesenberger and Capinpin exten­
reaction with gel effect. sively studied the behaviour of a non-isothermal
polymerization reactor, its sensitivity to the operating
conditions and the consequences of temperature vari­
ations on the conversion and molecular weight distri­
LITERATURE REVIEW ON NON-ISOTHERMAL bution. They classified the principal non-isothermal
POLYMERIZATION REACTIONS phenomena into run-away, ignition (parametrically
Exothermic polymerization reactions occurring in a sensitive run-away) and dead ending (incomplete con­
low thermal conductivity medium create a difficult version of the monomer due to initiator burning out
heat transfer problem which seriously limits achieve­ prematurely at high temperatures) (Biesenberger and
ment of isothermal conditions in tubular reactors. All Capinpin, 1974). A dimensional analysis inspired by
the rate constants of the elementary steps in a free­ explosion and combustion theories was also carried
radical mechanism are assumed to have an Arrhenius out by these authors. Using dimensionless groups, they
temperature dependence. However, the initiation pro­ derived criteria to predict run-away (RA), ignition (IG)
cess requires a much higher activation energy than and dead ending (DE) in non-isothermal polymeriz­
termination. An increase in temperature consequently ation. These predictions were compared with com­
affects kd much more than kt. Therefore, this strong puter simulations (Biesenberger et al., 1976) and with
positive feedback further accelerates the reactor tern- experiments (Sebastian and Biesenberger, 1976).

Table 2. Kinetic equations for the proposed free-radical mechanism

r:t a -kd I I l (1)

rR - 2fkd(IJ-k i[R0)(H] ( 2)

rM - -k1[R"] [MJ-(kp+kt };\0(M) ( 3)

m

k p [M] ( [ P,'.,- 1-(P.;_ J )-(kt

1 m
(M)+kt
s
I SJ} Ip�]-( p� IL
m�
k t IP.;, l (5)

( 6}

n-1

kt [P,'.,J [H]+kr [P.;_J [SJ+kt IP,;J:i..0+0.Skt L (P� I [P�ml (7)

m s d c m-1

with the symbols used in Table 1 and the following

no tations for the rate constants:

kd - initiator decomposition

k i - initiation

kp - propagation

ktm- transfer to monomer

kts - transfer to solvent

kc - termination by dis proportionation

d
k tc 'O
termination by combination
78 P. E. BAJLLAGOU and D. S. SooNG

The above modeling work was somewhat refined by kinetics is due to the reduction of the free volume of the
Brooks (1983) who showed that the boundary between mixture with conversion. This phenomenon, called gel
ignition and extinction can be more accurately located, effect, occurs even under isothermal conditions and is
if changes of densities and heat capacities with tem­ entirely different in nature from the previously dis­
perature are taken into account in the analysis. His cussed thermal autoaccelerations. The origin of the gel
conclusions are consistent with the important ideas effect was discovered by Trommsdorff (1947). The rate
already formulated by Biesenberger and co-workers. of polymerization is not accelerated by an increase of
Work done in the U.S.S,R. about non-isothermal the rate of initiation, but by a decrease of the rate of
polymerizations was reviewed by Stolin et al. (1979). termination. The termination steps are more severely
Again, the analogy with combustion theories allows diffusion controlled than the propagation reaction,
the utilization of Semenov and Frank Kamenetsky's because they involve reactions between macroradicals
work in the treatment of thermal effects on the free­ whose mobility is seriously reduced by the diminishing
radical polymerization kinetics. free volume of the polymerizing mixture. When the
Another cause of non-linearity in polymerization conversion in the reactive fluid approaches its glass

Table 3. Mass and energy balance equations for a plug-flow reactor at steady-state

dx
( l )
dz uz

d I Ij l duz
- --( r -(I)
1
-- ) ( 2)
dz uz dz

d l duz
---
ll.o
- --( r - ll.o -- ) ( 3)
dz ll.o dz
Uz

dT l
rT
( 4)
- -- ( -- )
dz Uz pcv

with:

rx � (kp+kt )(l-x)ll.0 ( 5)
m
r
I
- -kd [I} ( 6}
')
( 7}
-
rll.0 - 2fkd[ I )-kcll.0

rT - - AHpkp [M]ll.0+ (8)

where:

x conversion

(I] init:iator concentrat:ion

[M J .. monomer concentration
00

total_ radical concentration - L ( P�)

n-l.
T temperature of the reaction mixture
Tbath' temperature of the bat:h

axial_ ve1-ocity
uz
p density of t:he mixt:ure

Cv hea t capacity of the mixture

n� heat of pol_ymerization

U overall heat transfer coefficient bct�1cen the reaction riix t ur e

and the bath f 1-uid

H rhJrrtcteristic linear dir."':.cnsion .. volunc over tot:al heat t:rn.nsfer

area
 Free-radical polymerization 79

transition at the reaction temperature, movement of stants. Conservation of energy accounts for the heat
the monomer molecules is also impeded. The rate of generated by the propagation reaction and heat re­
propagation thus decreases and the reaction stops moval through the wall of the reactor and by convec­
before complete depletion of monomer or initiator. tive fluid flow. The gel effect is modeled by the
Accurate constitutive equations must be derived to constitutive equations derived by Chiu et al. (1983).
describe the dependence of the apparent propagation Volume contraction due to reaction as well as the
and termination rate constants on conversion, tem­ temperature dependence of the densities of monomer
perature and molecular weight. Several models have and solvent are allowed for in the model. The density
been proposed in the literature. These are reviewed by of the mixture is a function of the conversion, the
Carratt (1983). All models agree on the principle of amount of solvent introduced in the feed and the
relating the termination rate to macroradical diffusion. temperature. Heat capacities of the monomer, solvent
Differences exist in the choice of the theory to describe and polymer are taken to be constant, independent of
the diffusion processes. temperature. Monomer and polymer are assumed to
have the same heat capacity on a unit mass basis.
The complete mechanism of MMA polymerization
MODEL DERIVATION is summarized in Table 1. Application of simple kinetic
This model describes the non-isothermal bulk or laws to the polymerization mechanism allows the
solution polymerization of methyl methacrylate in a derivation of the rate of accumulation for the species
plug-flow reactor at steady state. Axial diffusive mass (Table 2). The rate of accumulation of the total
and heat transfer are neglected. Since the quasi-steady concentration of radicals l::'=i [P.] = A.0 [eq. (7),
state approximation is not used, three differential mass Table 2] was obtained by adding all the free radical
balance equations are required (conservation of kinetic equations.
monomer, initiator and total radical concentrations). The set of coupled first order differential equations
Non-isothermal effects are accommodated by coup­ is listed in Table 3. The Arrhenius temperature depen­
ling the mass balances to an energy balance equation dences of the rate constants are shown in Table 4.
through the Arrhenius expressions for the rate con- Table 5 gives the physical properties of the chemical

Table 4. Kinetic rate constants used in the models

f - 0.58

kd(min-1) • 6.32•1016 exp [-30.66 (kcal/mole}/RT(°K})

(Tobolsky and Baysal, 1953}

k p(l./min.mol) • 2.95•107 exp (-4.35 (kcal/mole)/RT(°K))

(Mahabacli and 01Drlscol 1, 1977)

k
t
m - 9.48•103 exp (-13.38 (kcal/mole)/RT(°K))
k
p
(Stickler and Meyerhoff, 1978).

k
t
8 1.01•10 3 exp [-11.40 (kcal/mole)/RT(°K))
k
•

p
(Gopalan and S anthappa, 1957).

k (I/min.mol) 9 exp (-0.701 (kcal/mole)/RT(°K))

t • 5.88•10

(Hahabadi and 01Driscoll, 1977).

k
t
c
- 3 .956•10-4 exp (4.09 (kcal/mo1e)/RT(°K))
�
(Be�ington, et al., 1954).
80 P. E. BAILLAGOU and D. s. SooNG

Table 5. Physical properties of the polymerizing mixture

MMA)
3
pH(g/cm ) 0.9665 0.0011 T(°C) (our data for

p8(g/cm )
3
0.883 0.0009 T(°C) (our data for to1uene)

-
C - - 0.1946 - 0.916•10 3 T(°C) (our data. assum:Lng

C (ca1/g• ° C) 0.4 (Ja�sLnghan� and Ray, 1977)

p
H

C (ca1/g•°C) 0.535 {Perry and ChL1ton, 1973)

p
s
WH(g/mo1) 100.13 (Weast, 1982)

w8(g/m.o1) 92.15 {Weast. 1982)

Table 6. Gel effect constitutive equations

w�th:

4
3. 46 • 10
4.4533 • 1018 [I]F exp(­ )
R{T+273 .15)

15 2. 8 • 10 4
2 • 5 29 2•10 exp ( - )
R(T+273.15)

(1 - 91p)
D - exp (2.303 ������ )
A + B(l )
-91p

A 0 .168

B 0.03

where:

TgpLB the g1ass transLtLon temperature of PMHA {ll4°C )

91 p �a the vo1ume fractLon of po1ym.er

 Free-radical polymerization 81

species involved in the process. The gel effect constitut­ Residence time (min)

ive equations are summarized in Table 6. 0 10 20 :30

This extremely stiff non-linear initial value problem (b)
180
is numerically integrated by Gear's method. The
RA
---
results of the calculation are the conversion, tempera­ 2
ture, initiator and radical concentration profiles. 3

160

4
RESULTS AND DISCUSSIONS
IG
Most of the previous modeling and experimental
efforts about polymerization kinetics were devoted to � 140 GE l

batch systems. Since plug-flow and batch reactor

models are mathematically equivalent, our results can
be easily reduced to the batch reactor frame in order to
check their agreement with previous studies. After
suitable transformation (multiplication of the right­
hand side of the plug-flow equations by Q/nR 2, Q
being the volumeti"ic flow rate and R the inner radius of
the reactor), this model gives predictions in complete
agreement with the work by Chiu et al. (1983) on
isothermal batch polymerizations. This confirms the
Axial distance (cm)
consistency between the numerical techniques and
basic equations of the two works. The non-isothermal
Residence lime (min)
simulations of this model are shown in Figs 1-5. This o 1 o 2or=------ 3 0
set of figures examines parameter sensitivity of the
1 0-<1 r______r_____� �,=-,
process in detail, including the effects of varying an Cc)
initial condition (feed temperature, concentration of
initiator or fraction of solvent in the feed) or a system
parameter (overall heat transfer coefficient through the
'
wall, or bath temperature). The horizontal axis can be ... 10
0
scaled either in residence time or distance. The distance .§.
scale chosen here corresponds to our experimental c:
.2
conditions, where the feed flow rate is 1 cm3 s -1 into a �
1 cm radius tube. The residence time scale allows ready c
Q)
u
use of the predictions for other tubular or batch c
8
reactors. 0
u
The results show the details of the transition from 'O
quasi-isothermal to run-away behaviour. With gentle e
Q)

feed conditions, the temperature profiles reach a low "'

plateau after a smooth maximum. As the initial

E 107
=>

E
(.)
=>

Residence time(minl
10>!-_____,.2.,.,_______�
. 0�______,
10
-8
10
<a>
0 200 400 600
0.8 Axial dis1ance (cm)

Fig. L Non-isothermal polymerization of MMA. Influence

of AIBN concentration in the feed on the conversion,
06 temperature and cumulative radical concentration profiles
0
c:
(or histories) simulated by a plug ftow (or batch reactor)
� model. U = 15 Btu/h ft2°F, s = 0, TF = 80°C, Tbath = 80°C.
...
> [AIBNJF (moljl): (1) 0.0320, (2) 0.0258, (3) 0.0226, (4) 0.0193,
(.) 04
c:
0 (5) 0.0177, (6) 0.0161, (7) 0.0129.

conditions become more severe, two temperature

0.2
maxima can be observed. The first peak is a de­
generated run-away, showing that the heat transfer is
barely sufficient to keep the temperature under con­
o �:.____...____,____,__---'=.h---1..----'
0 200 400 trol. The second maximum is induced by the gel effect.
E;iOC)
Axial distance fem] With increasing severity of the initial condition, the

CF.S 40:1-F
82 P. E. BAILLAGOU and D. s. SooNG

Residence time(minl Residence lime (min)

1.o o
;::-------''"'o'-------=2=,o;=:-______........,. 10-40r------•�o"-------2=ro_____�3�0
�
Ca> Cc)

c: c:
0 0
·;:
� �
Q)
> c
c: "'
0 ...,
(_) c::

8
0
'6
...,

e
"'

� 167
:::>

E
600
:::>

200 400 (_)

Axial distance (cm)

-a
10
Residence lime(minl
0
iscP.������'0��2�0'--���---"3�0,__. 200 400
Axial distance (cm I
600

(b)
Fig. 2. Non-isothermal polymerization of MMA. lnftuence
of the feed temperature on the conversion, temperature and
I
160 cumulative radical concentration profiles (or histories) simu­
IG 2 3
GEI 4 lated by a plug ftow (or batch reactor) model
GEi U = 15 Btu/h ft2 °F, [AIBN]F = 0.0258 mol/1, s = 0, Tbath
GEi
= 70°C. TF (0C): {1) 100, (2) 96, (3) 95, (4) 90, (5) 80.
140

and the hot spot is shifted towards the inlet of the

reactor until early run-aways are generated (Figs 4
and 5).
The conversion plots corroborate essentially the
same points observed in the temperature profiles.
Under gentle feed conditions, the conversion increases
linearly with the axial distance. If the conditions
become more severe, the conversion profiles show an
acceleration of the reaction near the outlet of the
0 400 600
reactor. This onset of non-linearity is shifted towards
Axial distance (cm)
the inlet of the reactor as the severity of the initial
conditions increases. The slope of the conversion
profiles suddenly becomes almost vertical until the
temperature profile suddenly becomes concave up­ conversion abruptly levels off, indicating initiator
wards and the temperature reaches a high, sharp burn-out and incomplete reaction.
maximum at the early stage of the reaction. The The radical concentration plots exhibit charac­
mixture then cools pff rapidly to the surrounding teristics consistent with the hot spots and non­
temperature, indicating that the reaction has stopped. linearities observed in the temperature and conversion
Further changes in the initial condition do not affect profiles. The early run-aways coincide with very rapid
the temperature profiles significantly (Figs 1-3). Under increases in the radical population followed almost
good heat transfer conditions, the temperature profile immediately by its total disappearance. A rapid growth
becomes ftat without exhibiting any initial maximum. of the radical population is also observed in the case of
An increase of the surrounding temperature or a hot spots generated at the end of the reaction.
decrease of the heat transfer coefficient causes the However, radical concentration does not entirely
temperature to stabilize at a higher level. Additional vanish, but levels off or even increases after the sharp
changes in the same direction cause the formation of a maximum. An interpretation of these observations will
hot spot close to the outlet of the reactor. Eventually, be proposed below based on analyses of polymeriz­
the breadth of the temperature plateau is shortened ation reactions previously reported in the literature.
 Free-radical polymerization 83

Residence Residence tm
i elminl

1.00 10 10-4 �0�����--'-;10"--=2�0'--��-3�0"'""'

(a) (C)

0.8
�
"' 10
Ci
.s
c
06
. c:
0 0
+=
� �
"'
> c
c Q)
0 04 u
u c
0
u
Ci
u
'O
0.2 e
...
-�
!2
:>

E
0 :>
0 200 400 600 u
Axial distance !cm)

-6
10

Residence timeCminl 0 200 400 600

d 10 20 30 Axial distance Ccml

(b) Fig. 3. Non-isothermal polymerization of MMA. Influence

160 of the weight fraction of solvent (toluene) in the feed on
the conversion, temperature and cumulative radical con­
centration profiles (or histories) simulated by a plug flow (or
batch reactor) model. U = 15 Btu/h ft2°F, [AIBN]F
160 = 0.0258 moljl, TF = 80°C, Tbat
h = 80°C. s; (1) 0.00, (2) 0.10,
(3) 0.15, (4) 0.20.

.t 140

�
:::> by Sebastian and Biesenberger (1978) who experimen­
0
tally observed the transition from controlled to un­
� �20
controlled operation caused by small variations of the
E
...
I- initiator concentration in the feed. Their experimental
temperature histories are quite similar to our simu­
100 lation results for the same conditions (Fig. 3). As the
initiator concentration in the feed increases, the tem­
perature maximum at the begining of the reactor
80 becomes more pronounced, and the peak suddenly
0 becomes much sharper. This first run-away is para­
AKiol distance (cm)
metrically sensitive and is therefore an ignition, ac­
cording to Biesenberger's terminology. The high acti­
vation energy of the initiator decomposition, re­
The control of reactor temperature can be easily lost sponsible for the strong temperature dependence of
during two delicate phases of the polymerization the rate of initiation, is the source of this parametric
process. At the beginning of the reaction, the radical sensitivity. However, further increases in the initiator
population builds up very rapidly, until a steady state is concentration do not alter the temperature maximum,
reached, at which point the loss of radical popuJation and change the location of the peak only slightly. The
by termination balances the rate of production by parametric sensitivity disappears and the hot spot
initiation [eq. (7), Table 3]. This rapid establishment of following ignition is simple run-away. A similar pat­
the radical population releases much heat in a narrow tern describes the influence of all other parameters of
region of the reactor. This is the major cause of the the process.
early run-aways described by Biesenberger. The tem­ The high temperatures generated during a run-away
perature plots (Figs 1-5) show that the transition to or an ignition considerably enhance the rate of in­
run-away behaviour can be induced by very small itiator depletion. The initiator concentration vanishes
changes in any of the parameters or operating con­ rapidly and causes depletion of the radical population.
ditions investigated here. This behaviour was reported The reaction stops by exhaustion of initiator before
84 P. E. BAILLAGOU and D. S. SooNG

Residence Residence time (min)

1.00 10 10-4 or-------'1,,o'---'2"'or-=3<ro�

Ca> Cc)
5
0.8
� 10
0
QJ

.§.
c:
06
0

·�
Cl>
>
c::
0
u
04

0.2

0
0 2'JO 400 600
A"-•al distance lcml

-6
10

Residence time{minl
0 200 400 600
10 20 30 Axial distance (cm)
0
RA
(b) Fig. 4. Non-isothermal polymerization of MMA. Influence
180 of the overall heat transfer coefficient on the conversion,
temperature and cumulative radical concentration profiles (or
2
IG histories) simulated by a plug flow (or batch reactor) model.
(AIBNJF = 0.0258 mol/J, s = 0, TF = 80°C, Tbath = 80°C.
160 U (Btu/h ft2 °F) (1) O, (2) 15, (3) 20, (4) 30, (5) 60, (6) oo .
5
4 GE!
3 GE!
GE!
� 140
� effect occurs at an advanced stage of the reaction when
:>

0 the concentration of reactants is low, the temperature

:g_ 120 rise and its consequences are less deleterious than the
E
"'
I- early run-aways or ignitions discussed above. The
radical population does not entirely disappear after a
gel effect induced hot spot, because the diminution of
k1 caused by the gel effect limits the rate of radical
termination [eq. (7), Table 3] . Dead ending is therefore
less severe, since part of the radical population survives
200 400 600 the hot spot, allowing the conversion to proceed
Axial rlistance (cm)
(although at a slower rate) beyond the gel effect
induced temperature rise.

total conversion of monomer is reached. This phenom­ CONCLUSIONS

enon of dead ending can be observed in the conversion Two entirely different mechanisms are found to be
curves (Figs 1-5) corresponding to uncontrolled tem­ responsible for the non-linearities exhibited by poly­
perature. It is particularly severe in cases of early run­ merization reactions. The hot spots observed in the
aways. When the radical population grows under simulations are attributed to either the rapid forma­
control, the temperature profile levels off to approach a tion of the radical population at the beginning of the
plateau, often after a broad, yet small maximum. The reaction or to the gel effect. The consequences of both
conversion increases gradually with distance when the phenomena are amplified by the positive feedback
temperature is steady. inherent in the kinetics. The existence of these two
The other difficult phase of the reaction occurs at the separate mechanisms inducing autoacceleration has
onset of gel effect. The heat generated by the autoac­ not been clearly identified in the literature. Pre­
celeration of the· reaction causes the temperature to vious studies about non-isothermal polymeriz­
rise. Gel effect induced (labeled GEI on the plots) run­ ation (Biesenberger and Capinpin, 1974; Biesenberger
aways are not parametrically sensitive. Since the gel et al., 1976; Brooks, 1983) ignore or neglect the gel
 Free-radical polymerization 85

Residence time (mini Residence time (mini

LOO
10 20
-4
10 or=-
---''"'o"---=2.,,0'---'3::;;0�
Co) Cc)

08
4
�
"' 10
0
0.6 s
0
c:
<=
0
�
� �
Q,)
> c:
"'
c:
0 04 '-'
u <=
0
'-'
0

-c
v

0.2 e
.,
>
� -7
S! 10
:::>

E
0 :::>
0 200 400 600 u
Axial distance Ccml

Residence time (min l 0 200 400 600

� 0'----
1800 ------'1
�
- ----'2
�o;:o...____
. --=3�0'""' Axial distance (cm)

Cb) Fig. 5. Non-isothermal polymerization of MMA. Influence

RA 5 of the bath temperature on the conversion, temperature and
EI cumulative radical concentration profiles (or histories)
160
simulated by a plug flow (or batch reactor) model.
U = 15 Btu/h ft2 °F, [AIBN]F = 0.0258 molfl, s = 0, TF
= 70°C. Tbath (0C): (1) 80, (2) 77, (3) 76, (4) 75, (5) 72.5, (6) 70.

pattern in a tubular reactor. Experimental results will

be compared with predictions of the extended models
in future publications.

Acknowledgement-This work was supported by the

National Science Foundation via CPE 8103632.

600
Axial distance (cm) REFERENCES
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