Ind. Eng. Chem. Res.

2008, 47, 90619071

9061

Polymerizations in the Presence of Vaporization: Experimental Results on Nylon-6

Manojkumar Ramteke and Santosh K. Gupta*
Department of Chemical Engineering, Indian Institute of Technology, Kanpur 208016, India

This study deals with the hydrolytic step-growth polymerization of -caprolactam to produce nylon-6 in a
semibatch reactor at near industrial conditions. -caprolactam is polymerized in a 1.6 L stainless steel reactor
at three different initial water concentrations, 4.43% (by mass), 2.52%, and 3.45%, respectively. During the
polymerization, the values of the temperature and the pressure are controlled and recorded. Samples of the
liquid reaction mass are taken from the reactor at different times and analyzed. The monomer conversions
are obtained gravimetrically (in terms of water extractibles) as well as by using gas chromatography. The
samples are also analyzed for the degree of polymerization using amide and acid end-group concentrations.
The parameters are tuned using one set of data with genetic algorithm. The tuned parameters are then used
to predict the second set of data. In the simulation, the poly-NRTL model is used to describe the vapor-liquid
equilibria. The simulated values match well with the experimental values. The tuned model gives reasonably
good results.
Introduction
Several industrial polymerizations of commodity and specialty
plastics, e.g., nylons, polyethylene terephthalate, polycarbonates,
etc., involve the vaporization of low molecular weight compounds. Reaction engineering principles and information are
reasonably well-established for the liquid-phase kinetics of these
systems. However, information on the vapor-liquid equilibrium
(VLE) and mass transfer aspects for such systems are not as
well-developed. Some experimental data are available in the
open literature, e.g., Giori and Hayes1,2 for nylon-6, on the VLE
of polymer-monomer-solvent systems in the absence of
polymerization, but the experimental scatter is considerable. The
Flory-Huggins theory,3 with a curve-fitted value of the 1
parameter, has been used by Laubriet et al.4 for modeling
vaporization in wiped-film PET reactors. More recently, Seavey
et al.5,6 have applied the poly-NRTL model7 to the nylon-6-caprolactam-water system and have analyzed the data of Giori
and Hayes1,2 to tune the model parameters. They then carry
out the simulation of an industrial nylon-6 reactor train but do
not provide any industrial data for proprietary reasons. A better
method for tuning model parameters characterizing VLE is to
use experimental/industrial data on polymerizing systems. This
is the focus of the present study. Four sets of experimental data
have been generated for nylon-6 polymerization under nearindustrial conditions and in the presence of vaporization, and
the data have been used to better our understanding of such
reactors. The methodology is quite general, and the knowledge
gained can easily be used for studying other systems.
Most of the nylon-6 plants use the hydrolytic polymerization
process.8,9 This process consists of the polymerization of
-caprolactam (C1 or CL) in the presence of water (W) at
temperatures ranging from 230 to 280 C. Water is used to open
the -caprolactam ring (reversibly) to give a linear bifunctional
molecule, aminocaproic acid (ACA, S1; see Table 1). Polymerization then proceeds by the step-growth mechanism to give
linear polymers (Sn; n ) 1, 2,...), with water as the condensation
byproduct. In addition to these reactions, the amino end-group
of any linear polymer molecule (Sn) can also open the -caprolactam ring reversibly. This is the polyaddition reaction. The

linear dimer, S2, however, can cyclize reversibly to form cyclic

dimer (C2). The amino end-group of any linear polymer (Sn)
can attack a molecule of the cyclic dimer and add it on, giving
a longer linear molecule (Sn+2). Higher cyclic oligomers (C3,
Table 1. Kinetic Scheme of Nylon-6 Polymerization

* To whom correspondence should be addressed. E-mail: skgupta@

iitk.ac.in. Tel.: 91-512-259 7031; 7127. Fax: 91-512-259 0104.
10.1021/ie800287d CCC: $40.75 2008 American Chemical Society
Published on Web 07/03/2008

9062 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
Table 2. Rate and Equilibrium Constants11,12

Ai0 (kg/(mol h))

Ei0 (J/mol)

1
2
3a
3b
3c
4
5

5.9874 10
1.8942 1010
2.8558 109
2.8558 109
2.8558 109
8.5778 1011
2.5701 108

8.3198 10
9.7389 104
9.5606 104
9.5606 104
9.5606 104
1.7577 105
8.9141 104

Aic (kg2/(mol2 h)
4

4.3075 10
1.2114 1010
1.6377 1010
1.6377 1010
1.6377 1010
2.3307 1012
3.0110 109
7

Eic (J/mol)

Hi(J/mol)

7.8703 10
8.6504 104
8.4148 104
7.5733 104
8.4182 104
1.5652 105
8.5374 104
4

Si(J/(mol K))

8.0268 10
-2.4883 104
-1.6923 104
-1.5231 104
-1.5150 104
-4.0176 104
-1.3263 104
3

-3.2997 101
3.9496 10
-2.9068 101
-2.9068 101
-2.9068 101
-6.0766 101
-2.4384 10

Values from Tai et al.11 b Values from Wajge et al.12 c This work.

Figure 1. Schematic of the reactor assembly.

Table 3. Details of the Four Experimental Runs
values

variable
[C1]0
(mol kg-1)
[W]0
(mol kg-1)
F (kg)
[Nv]0
(mol m-3)
Dr (m)
ds (m)
103 Vg (m3)
a

Run 1a
Run 2
Run 1
(near-replicate)
[W]0 ) 4.43%a [W]0 ) 4.43% [W]0 ) 3.45%

Run 3
[W]0 )
2.52%

8.458

8.458

8.544

8.627

2.461

2.461

1.917

1.40

0.522
59.56 (N2)

0.622
84.36 (Ar)

0.600
81.56 (Ar)

0. 586
81.56 (N2)

0.109
0.105
1.358

0.109
0.105
1.2

0.109
0.105
1.2056

0.109
0.105
1.2456

Mass fraction.

C4,...) are also formed, but these are not included in Table 1
since their concentrations are much smaller, and data on their
rates of formation are not available. This table also does not
include side-reactions like decarboxylation, desamination, and
peroxidation of the -caprolactam.

Hydrolytic polymerization is usually carried out until nearequilibrium conditions. The quantity of monomer present in the
equilibrium polymer product depends upon the reaction temperature and the amount of water present in the reaction mass.
Under industrial conditions, the amount of residual monomer
present in the polymer is about 8-9%, while that of the cyclic
oligomers is about 3-6%. It is necessary to remove the
monomer, water, and cyclic oligomers from the product since
the subsequent processing of the polymer is adversely affected
by their presence. This is achieved by a hot water extraction
process or vacuum evaporation.
Several studies have been reported on nylon-6 polymerization.
Reimschuessel8 and his group were among the early workers
in the field. This group described the mechanism and the kinetics
of polymerization and reported values of several rate constants.
Their constants, however, were estimated using only a small
amount of experimental data. They did not measure the
concentration of aminocaproic acid (they estimated the equilibrium concentration of S1 from the equilibrium end-group
concentration and the number-average degree of polymerization
by assuming a Flory-Schulz distribution3,9). In fact, very little

Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9063

Figure 2. Experimental data and model predictions for [W]0 ) 4.43% (Run 1).

Figure 3. Experimental data and model predictions for [W]0 ) 3.45% (Run 2).

data on the concentration of S1 exists under a variety of

experimental conditions except those of Hermans et al.,10 and
that, too, under comparatively limited conditions. Tai and
Tagawa11 carried out a very extensive study of nylon-6
polymerization in sealed tubes under isothermal conditions
(230-280 C) and with several initial concentrations (0.421-1.18

mol/kg) of water. They measured the concentrations of aminocaproic acid by high-pressure liquid chromatography, of
-NH2 and -COOH end-groups by titration, and of the cyclic
dimer by gas chromatography. They found that the rate constants
depend upon the initial water concentrations to some extent.
Average values of the rate constants, useful over a limited

9064 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008

Figure 4. Experimental data and model predictions for [W]0 ) 2.52% (Run 3).

Figure 5. Experimental data and model predictions for the near-replicate Run 1a ([W]0 ) 4.43%).

though relevant range of initial water concentrations (0.42-1.18

mol/kg), have been reported. These11 are listed in Table 2 along
with recently updated values.12 It is observed from Tables 1
and 2 that all the reactions are reversible and catalyzed by the
carboxyl end-groups of the polymer chains. The Arrhenius form
is used for both k0i and kci , the rate constants for the uncatalyzed

and catalyzed components of ki, respectively. The equilibrium

constants are expressed in terms of the enthalpies and entropies
of reaction.
Recently, Mallon and Ray13 applied a more fundamental
approach to fit the data11,14 in the literature. They assumed that
the water in the nylon melt is present in two forms: the bridged

Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9065
Table 4. Error Analysis of Run 1a
t (h)

grav
Xm

0.933
1.550
2.089
3.017
4.033
5.033
6.033
7.033
8.017
9.017
10.000
11.083
12.050
13.060
14.000
14.585

0
0.7322 ( 1.08 10-4
0.8638 ( 1.17 10-4
0.8553 ( 1.17 10-4
0.8427 ( 1.16 10-4
0.8558 ( 1.15 10-4
0.8426 ( 1.17 10-4
0.8480 ( 1.15 10-4
0.8426 ( 1.16 10-4
0.8372 ( 1.16 10-4
0.8367 ( 1.14 10-4
0.8371 ( 1.15 10-4
0.8365 ( 1.16 10-4
0.8335 ( 1.14 10-4
0.8455 ( 1.16 10-4
0.8457 ( 1.14 10-4

n (amide)
34.96 ( 0.48
45.85 ( 0.65
52.30 ( 0.77
53.50 ( 0.82
58.12 ( 0.95
61.63 ( 1.10
63.97 ( 1.45
57.79 ( 1.45
62.79 ( 1.86
71.50 ( 1.47
76.58 ( 2.79
97.22 ( 2.74
104.42 ( 4.74
143.00 ( 4.99

n (acid)
30.43 ( 0.49
46.21 ( 0.84
53.42 ( 1.22
52.66 ( 1.20
53.59 ( 1.25
62.12 ( 1.95
59.95 ( 1.82
61.20 ( 2.27
64.71 ( 2.59
68.41 ( 3.43
72.51 ( 3.16
81.98 ( 2.42
105.27 ( 7.65
126.63 ( 6.04

and the free forms. Only the free water takes part in the
polymerization. Schaffer et al.15 carried out similar experiments
on nylon-6-12.
Gupta and co-workers9,12,16,17 have reported several studies
on the modeling of nylon-6 reactors. One of these is on an
industrial semibatch reactor (see Figure 1), in which C1 and W
vaporize and build up the pressure in the (closed) vapor space
above the liquid reaction mass. The vapors are released later
so as to lower the pressure in a programmed manner. This
controls the liquid-phase concentration of W and, thus, controls
the rate of polymerization (the initial concentration of W in the
liquid is kept high so as to speed up the ring-opening step and
is lowered subsequently to drive the reversible polymerization
in the forward direction). Unfortunately, trustworthy industrial
data was available to us only for three initial water concentrations. The temperature histories, T(t) (for a constant jacket
fluid temperature, TJ) were available for these three runs, as
were the pressure histories, P(t) [the latter was controlled, so
only the part before the release of vapors was useful for
parameter estimation]. In addition, the final values of the
monomer conversion and the number-average chain length were
available (instead of the values at several intermediate times)
for the three cases. This was insufficient to tune, properly,
the parameters used in the simulation model,12,17 particularly
those associated with the rates of vaporization of C1 and W.
This was a severe handicap. In fact, very little experimental/
industrial data are available in the open literature to estimate
the parameters describing the rates of vaporization in any
polymerization reactor. The present study generates experimental
data on a 1.6 L stainless steel nylon-6 reactor in which
vaporization and vapor release take place continuously so as to
achieve a desired pressure history. Samples of the liquid are
taken at different times during the polymerization. The liquid
samples are analyzed using gas chromatography, gravimetric
analysis, and end-group analysis to give the number-average
molecular weight, Mn, of the polymer and the monomer
conversion, Xm. Our detailed experimental study provides more
data to carry out a meaningful fitting of the model12 parameters.
Experimental Details
Design of the Reactor. The reactor used in this study is
specially designed to carry out the polymerization of nylon-6
at temperatures of about 250 C. A 1.6 L semibatch 304-stainless
steel (SS) reactor is used (see Figure 1). The reactor is mounted
on a movable aluminum trolley. A 2000 W electric heater is
wound around the reactor. This is insulated on the outside with
asbestos rope. There are several SS pipes connected to the

reactor head. One (0.64 cm ) is fitted with a needle valve (N2

in Figure 1), which controls the rate of release of vapor and,
thus, the pressure inside the reactor. Two more openings in the
reactor head include one for feeding inert nitrogen or argon to
the reactor through the needle valve (N1 in Figure 1) [the
nitrogen/Ar exits through the needle valve (N2) during purging]
and the other for charging the monomer/water. The latter is
closed by a SS stopper. The reactor is fitted with a pivoted
anchor stirrer, a thermowell, and a pressure gauge (0-14 kg/
cm2 on the inlet nitrogen/argon line). A calibrated J-type
(iron-constantan) thermocouple is used to measure the temperature of the liquid inside the reactor continuously. The
temperature of the reaction mass is controlled by a timeproportioned proportional-integral-derivative (PID) controller
(Fusi Electricals, Japan). The stirrer is operated by a 0.187 kW
motor and its speed is measured by a digital tachometer. A ball
valve (V1) is fitted on another SS tube on the reactor head. This
tube is open at the bottom and dips into the reaction mass. A
250 W heating tape is wound around this tube outside the
reactor. This tube is used for taking out samples at the beginning
when the reaction mass is not too viscous. There is an opening
at the bottom of the reactor connected to a 1.4 cm o.d. SS pipe
with a ball valve (V2). This is used to take out polymer samples
during later stages of polymerization when the reaction mass
is more viscous. This is also wrapped with a 250 W heating
tape. The first two (initial) samples are taken out through the
ball valve V1 while the remaining samples are taken out through
the ball valve V2. This is because the viscosity of the polymer
in the early stages is low and the pressure inside the reactor is
quite high. If these early samples are taken out through the valve
V2, it would lead to a very rapid and complete draining of the
liquid from the reactor. The liquid samples are taken out
periodically from the reactor over short periods of time in empty
beakers that have been chilled in ice-water.
Raw Materials. -Caprolactam and water are the main raw
materials for the production of nylon-6. GC-grade (purity
>98%) -caprolactam (Fluka, Belgium) is used without further
purification, along with double-distilled water. meta-Cresol
(Loba Chemicals, Mumbai, India) having a purity greater than
98% is used. Extrapure-grade benzyl alcohol (Qualigens,
Mumbai, India) having a purity greater than 98.5% is used in
the analysis. Ethylene glycol (Qualigens, Mumbai, India) having
a purity greater than 98% is used.
Polymerization. A measured amount of solid -caprolactam
(>500 g) is put inside the reactor when it is in the tilted position
so that the solid does not fill up the seat of the pivot at the
bottom of the stirrer. The reactor is then made vertical, with
the head placed on top and sealed. The remaining C1 and the
prescribed amount of W are introduced through the opening in
the head, which is then closed using the SS stopper. The contents
of the sealed reactor are flushed four times using either nitrogen
(Grade-I, Pawan Gases, Kanpur, India) or argon (Grade-I, Pawan
Gases, Kanpur, India). Initially, a (gauge) pressure around 101
kPa of nitrogen/argon is maintained in the reactor. The reactor
is then heated (over about 38 min) to 245 C. Thereafter, the
temperature is maintained constant using the controller. The
temperature of the molten reaction mass is measured by a
calibrated J-type thermocouple. The -caprolactam starts melting
as the temperature increases. Since the melting point of
-caprolactam is 69 C, the stirrer is started as soon as the
temperature of the reaction mass goes above this value. The
stirrer speed is about 100 rpm at the start of a run and decreases
to about 40 rpm near the end. As the reaction proceeds, the
pressure builds up in the vapor space as -caprolactam and water

9066 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
Table 5. Mass Balance and Moment Equations12

vaporize while there is no release of vapors. High water

concentrations are required at the beginning of the process, while
low water contents are needed toward the end so as to drive
the polycondensation reaction forward and obtain nylon-6 having
a high value of Mn. To achieve this, the reactor is operated in
five different stages. In the first stage, the pressure is allowed
to build up to a set value with the needle valve (N2) closed. In
the second stage, the needle valve is opened in such a way that
the pressure remains almost constant for a desired period.
In the third, fourth, and fifth stages, the needle valve is operated
in such a way that the pressure drops (with three different slopes
of the pressure with respect to time). The pressure is recorded
periodically over time. The pressure history is similar to that
used industrially.12
Temperature Control. A time-proportioned PID controller
is used to control the temperature of the reaction mass. The
temperature is measured by a calibrated J-type thermocouple
inserted in the thermowell. The controller is operated in the
autotuned mode. Autotuning is done using silicone oil (370-390
mPa s at 20 C) in the reactor at 200 C. The tuned parameters
are given below:
(1) Proportional band (P) ) 11.6
(2) Integral action time (I) ) 906 s
(3) Derivative action time (D) ) 174.3 s
(4) Proportional time cycle (TC) ) 30 s
(5) Insensitive zone (HYS) ) 2%

Analytical Procedure. Gravimetry11 is used to analyse the

polymer samples. The quenched (solid) polymer samples
collected in the chilled beakers are crushed to a powder by a
hammer or shaved by a drill. The weighed samples are then
extracted with 20 times their weight of freshly distilled water
at 80 C for 4 h in an oven, after which they are filtered onto
weighed filter papers (No. 42, Whatman, Maidstone, U.K.) and
dried to a constant weight by heating to 105 C at 1 atm pressure
in an oven. Under these conditions, extraction equilibrium can
be assumed to have been achieved, and the hydrolysis of C1 to
S1 is negligibly small. The total hot water-soluble content is
equal to the loss in weight of the sample caused by extraction.
grav
Thus, the gravimetric conversion, Xm
, is given by
Xgrav
m )
)

weight of dried polymer sample after extraction

weight of polymer sample before extraction
kg of (only) polymer produced
kg of C1,W used (corrected for vaporization)

(1)

The liquid hot-water extract is analyzed to get the concentration

of the unreacted -caprolactam and the monomer conversion,
GC 11
Xm
. A Nucon-5765 (Nucon, New Delhi, India) gas chromatograph (GC) equipped with a dual-flame ionization detector
is used for the analysis of C1. The GC is fitted with a 1 m long
stainless steel column packed with Tenax GC of 80/60-mesh
size11 (Josco, New Delhi, India). Nitrogen (Grade-I, Sigma Gas

Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9067

Service, New Delhi, India) is used as the carrier gas. In the

analysis, the oven temperature is set at 200 C and the carrier
gas flow rate is set at 30 mL/min. The inlet temperature is
maintained at 230 C. A Hamilton (Hamilton, Reno, NV)
microliter syringe is used. Generally, 0.5 L samples are
analyzed each time.
The peak for C1 is observed to occur at 38 s. Initially, a
sample of known concentration (made by dissolving a known
amount of C1 in 100 mL of water) is analyzed. The area for
this sample is used as a calibration for the calculation of the
concentration of C1 in the extract, and then the total mass of C1
GC
in the extract is obtained. The monomer conversion, Xm
, is
calculated using
Table 6. Correlations and Equations Used5,6,12,2125a

Note: Additional details can be found in refs 12, 17, and 25.

XGC
m ) 1)

mass of caprolactam in extract

mass of polymeric sample before extraction

kg of polymer and C2 produced

kg of C1,W used (corrected for vaporization)

)
(2)

Molecular Weight Determination. The end-group analysis

technique1820 is used commonly for the determination of the
number-average molecular weights of condensation polymers.
The molecular weights of linear condensation polymers are
normally below about 20 000, and end-group methods are quite
accurate for such ranges. It is possible to estimate the concentration of the end-groups by chemical analysis and use these to

9068 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008
Table 7. Poly-NRTL5,6 and Poly-NRF21 Parameters for the
Water--Caprolactam-Nylon-6 System (Randomness Factor (rij) )
0.3)
component i/j
interaction
parameters

water/
-caprolactam

-caprolactam/
nylon-6 segment

water/
nylon-6 segment

Poly-NRTL Model5,6
-0.313
0.628
-15.4
-13.7
0.0495
-0.0898

aij
aji
bij
bji
cij
cji

0
0
297
-601
0
0

0
0
265
207
0
0

dissolved in 60 mL of benzyl alcohol at 150 C. The solution

is then titrated against a 0.02 N potassium hydroxide solution
with ethylene glycol, using phenolphthalein as the indicator, at
this temperature. The correct normality of a glycol-KOH
solution used for analysis is found by titrating with a standard
base solution.
The following equation19 is used to compute Mn using either
of the two methods:
Mn )

(sample weight 1000)

(titervolume [mL] normality)

n )

Mn
(3)
M0

where M0 is the molecular weight of the repeat unit () 113).

Poly-NRF Model (tuned; this study)

-0.336
0.596
-16.399
-13.993
0.033
-0.083

aij
aji
bij
bji
cij
cji

0
0
287.773
-604.632
0
0

0
0
269.528
197.242
0
0

Table 8. GA Parameters Used for Tuning

parameter

value

Np
Pcross
Pmut
Ngen,max
lchr
Nseed
w1
w2
w3

20
0.9
0.05
20
60
0.889
100
1
1

Table 9. Bounds and the Optimal Values of the Parameters

no.

parameter

lower limit

upper limit

tuned

Kinetic Parameters (Poly-NRTL)

(10-4 E3c) (J/mol)
(-10-4 H3) (J/mol)

1
2
3

7.5312
1.4770
0.001

8.7864
1.5983
0.005

8.4182
1.5150
0.0011

Poly-NRF Parametersa
1
2
3
4
5
6
7
8
9
10
a

-0.25
0.5
-12.0
-10.0
0.03
-0.08
280.0
-590.0
240.0
190.0

a32
a23
b32
b23
c32
c23
b31
b13
b21
b12

-0.35
0.6
-18.0
-15.0
0.06
-0.10
310.0
-610.0
270.0
210.0

-0.336
0.596
-16.399
-13.993
0.033
-0.083
287.773
-604.632
269.528
197.242

Table 10. Statistical Analysis of the Two Models

R2 value
poly-NRTL
run no.
1
1a
2
3

n
0.9003
0.8657
0.9551
0.7713

Xm

0.9852
0.8177
0.9853
0.9906

poly-NRF
Xm

GC

0.3662
0.9924
0.0207

Experimental Results. In this study, three polymerization

runs (and a near-replicate of one run) are carried out with initial
water concentrations of 4.43%, 2.52%, and 3.45% (w/w),
respectively. The details of these experiments are given in Table
3. The temperature and the pressure are recorded during
polymerization. The near-isothermal set-point temperature (set
point ) 245 C) and the pressure histories are maintained similar
to those used in the industrial reactor.12 These experimental
histories are shown in Figures 25 for the three values of [W]0.
The temperature of the reaction mass increases from about 21
to 245 C in about 38 min and then remains almost constant.
Figures 25 also show the experimental results for the two
GC
grav
conversions, Xm
and Xm
, as well as the experimental values
of n obtained using the amide and/or acid end-group concentraGC
tions. It is observed that the values of Xm
are slightly higher
grav
than (or almost equal to) those of Xm
, as expected from eqs
1 and 2. Also, the values of n obtained using the concentrations
of the two end-groups are in good agreement (in cases for which
both are carried out). The information on the errors is given for
Run No. 1a in Table 4. The errors in the values of the monomer
conversion are below about 1%, while those for n are below
about 3.5% for most cases.
Modeling. The kinetic scheme and the corresponding rate
constants for nylon-6 polymerization have already been discussed earlier and are given in Tables 1 and 2. The modeling
of such reactors12 poses severe problems primarily because of
lack of good correlations to model the vaporization of C1 and
W. Indeed, the following empirical equations have been used
in our earlier studies12,17 to model the activity coefficients of
the monomer, C1 (m), and water (w) for this reactor
mf - mo
(monomer conversion)w
0.95
wf - wo
(monomer conversion)
(4)
) wo +
0.95
In eq 4, mo, mf, wo, and wf are curve-fit parameters, which
were tuned earlier12 to explain the (small amount of) available
industrial data.
In the present study, two models that are more detailed,
namely, the poly-NRTL7 and the poly-NRF21 (nonrandom
factor) models, are used instead of eq 4 to describe the
vapor-liquid equilibrium at the interface of the vapor and the
liquid reaction mixture. Tables 5 and 65,6,12,2125 summarize
the complete set of model equations with these two models
incorporated. The parameters of the poly-NRTL model are taken
from Seavy et al.,5,6 while the parameters of the poly-NRF
model have been tuned in this study. These are given in Table
7. In both the models, the entropic contribution is calculated
using the Flory-Huggins equation (eq T6-g in Table 6). The
m ) mo +

Polymer (1)-caprolactam (2)-water (3).

grav

Results and Discussion

Xmgrav

XmGC

0.9020
0.8662
0.9542
0.7729

0.9850
0.8180
0.9848
0.9907

0.3693
0.9925
0.0161

estimate the value of Mn. In the amide end-group method, the

polymer is dissolved using phenolic solvents. m-Cresol (60 mL)
is used to dissolve 0.5 g of polymer. Methanol (20 mL) and
water (10 mL) are added to ensure that the solution is
homogeneous. The titrant is 0.02 N aqueous hydrochloric acid,
and the indicator is a neutral 0.1% solution of thymol blue in
water. In the acid end-group method, 0.5 g of the polymer is

Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008 9069

enthalpic contributions are calculated using the NRTL (eq T6e) or the NRF (eq T6-f) models for the two cases. These two
contributions are added to give the final expressions for m and
w (eq T6-h). The temperature dependence is built-in in terms
of the interaction parameter, ij (eq T6-i), in the two models.
The interfacial concentrations of C1 and water are calculated
using eqs T6-a-T6-c. These equations involve the activity
coefficients. It is assumed that the gas-phase resistances are
negligible. The same method cannot be used for calculating the
interfacial concentration of the polymer (an information piece
needed in the poly-NRTL/NRF models). We assume, empirically, that the interfacial concentration of the polymer is times
its bulk (liquid-phase) concentration, i.e., 0* ) 0, where
is an empirical parameter. Since the polymer molecules are
large compared to the sizes of the monomer and water
molecules, the concentration of the polymer at the interface will
be very low so that there is no vaporization (there is some kind
of an inconsistency in this argument since then there should be
mass transfer from the bulk of the liquid to the interface, but
there is no vaporization of the polymer). The parameter, , is
expected to be small and will be a function of the rpm of the
stirrer, as well as the size and geometry of the reactor. This
parameter is estimated (tuned) by minimizing the mismatch
between experimental data and model-predicted values (as
explained in the next section). An increase in the value of
leads to lower amounts of vaporization of the monomer and
water, but the sensitivity is small. An iterative procedure
(successive substitutions/Picard iteration) is required to compute
the activity coefficients since the interface concentrations
themselves are functions of the activity coefficients. The activity
coefficients, m and w, are first assumed. These are used to
calculate the interfacial concentrations (eqs T6-a-T6-c). The
latter are then used to recalculate m and w using eqs T6-e-T6j. If the mismatch between either of the calculated and assumed
values is >0.0005, the iterations continue. The activity coefficients are evaluated at time t, using the experimental values
of the temperature and pressure at that time (this enables the
successful convergence of the iterative scheme).
The detailed model is given in Tables 5 and 6. Most of the
equations (except those describing the vapor-liquid equilibrium
using the poly-NRTL/NRF model) are the same as given in our
earlier papers.12,17 Table 5 consists of 14 ordinary differential
equations (ODEs) of the initial-value kind (mass balances and
moment equations) that describe the system completely. In
addition to these, several correlations describing the vaporization
of low-molecular-weight species and various physical properties
like viscosity, vapor pressure, density of the reaction mass, etc.
are required for integrating these stiff ODEs. These are given
in Table 6.12,17 The driving force for the vaporization is the
difference between the concentration in the bulk of the liquid
reaction mass and that at the interface. The interfacial concentrations are calculated using eqs T6-a-T6-d. The reactions are
driven in the forward direction by vaporization that takes place
by two phenomena, namely, quiescent and bubbly desorption.
In quiescent desorption, water and -caprolactam vaporize from
the surface of the reaction mass at the top. In bubbly desorption,
bubbles of low-molecular-weight species (water and -caprolactam) form in the entire bulk of the reaction mass by
supersaturation of the liquid phase associated with the increase
in temperature, and then these bubbles rise to the surface. Bubbly
desorption is further divided into low- and high-bubbly regimes.
Above the critical relative supersaturation, c, the high-bubbly
regime starts. A more detailed description of these mass transfer
correlations is given in ref 25. The effect of temperature on the

various physical properties of the mixture is also given in Table

6. The stiff ODEs given in Table 5 are integrated using the
D02EJF subroutine (based on Gears algorithm) of the NAG
library. A tolerance, TOL, of 10-7 is used.
Parameter Estimation. The experimental temperature and
pressure histories are used as inputs in the model to obtain the
model-predicted (simulated) results. The equations in Tables 5
and 6 are used to obtain the model-predicted values. Data on
GC
grav
Xm
, Xm
, and n for only one run, namely, for [W]0 ) 4.43%
(Run No. 1), are used for tuning the parameters. Single-objective
genetic algorithm (GA) is used to minimize the weighted
normalized sum-of-square deviations of
(a) the experimental (subscript, expt) values of n,
GC
(b) the monomer conversion, Xm
, obtained using GC, and
grav
(c) the gravimetric conversion, Xm
from the model-predicted (subscript, sim) values:
ND

min I ) w1

i)1

n,expt - n,sim
n,expt

NC

+ w2

i)1

GC
XGC
m,expt - Xm,sim

NC

w3

i)1

XGC
m,expt

grav
Xgrav
m,expt - Xm,sim

Xgrav
m,expt

(5)

In eq 5, ND and NC are the number of experimental data points

available for n and the conversions, respectively. w1, w2, and
w3 are the weightage factors.
The tuning of the parameters is carried out in two stages.
The poly-NRTL model is used in the first stage. Different sets
of parameters from among the several in Table 6 are tried for
tuning, and finally three (the ones to which the results are most
sensitive) are identified that give the best agreement: two
parameters, Ec3 and H3, characterizing the polyaddition reaction,
and (the results were found to be much less sensitive to the
NRTL parameters). Since the kinetic parameters reported by
Tai and Tagawa11 in Table 2 are averaged over several initial
water concentrations, and since the values in the present study
lie outside this range, the two most sensitive kinetic parameters
are used for tuning. The best set of computational parameters
used in the GA code and obtained by trial is given in Table 8,
along with the weightage factors, while the upper and lower
bounds used for the three parameters are given in Table 9. Table
9 also gives the tuned values of these parameters. These three
tuned parameters are then used unchanged (so as to ensure that
the same kinetic constants are used in both the VLE models) to
obtain the 10 interaction parameters of the poly-NRF model.
The same objective function as given in eq 5 is used. The bounds
of these as well as the tuned values are given in Table 9 (the
latter are also given in Table 7). It may be emphasized that the
parameters of the poly-NRF model for the system nylon6-caprolactam-water are being reported for the first time.
Predictions of the Tuned Model. The model-predicted
results using the tuned parameters and the poly-NRTL model
are shown in Figure 2 for Run No. 1 ([W]0 ) 4.43%). These
tuned parameters are then used unchanged to predict the results
for the other three runs. The model-predicted results are shown
in Figures 35. It is observed that the experimental results are
in reasonable accord with the model predictions, except for n
near the final stages of polymerization. Possibly, diffusional
resistance26 assumes importance during this stage (and the
apparent rate constants change with time). The results of
the tuned poly-NRF model are almost indistinguishable from
those obtained with the poly-NRTL model. Table 10 compares
the two models using R2 values. It is observed that the
predictions of the two models are nearly the same. The
grav
predictions of n and Xm
are quite good. However, the low

9070 Ind. Eng. Chem. Res., Vol. 47, No. 23, 2008

values of R2 for XGC

m for all cases except Run No. 2 are because
of the significant deviations of a few initial experimental points.
Conclusions
Four sets of polymerizations of nylon-6 have been carried
out at three different initial water concentrations. These
polymerizations are associated with the simultaneous vaporization of two low-molecular-weight compounds. Either the polyNRTL or the poly-NRF models can be used to describe the
vapor-liquid equilibrium. The polymerizations are carried out
using pressure and temperature histories that are similar to those
used in industry. Experimental data on only one run, namely,
for [W]0 ) 4.43%, are used to obtain the best-fit (tuned) values
of the parameters. The tuned model is then used unchanged to
predict the other results. Reasonable agreement is observed for
the monomer conversion, the conversion of the hot waterextractible material, and the number-average chain length.
Acknowledgment
We dedicate this paper to Professor Arvind Varma. Financial
support from the Department of Science and Technology,
Government of India, New Delhi (through Grant SR/S3/CE/
46/2005-SERC-Engg, dated November 29, 2005), is gratefully
acknowledged.
Nomenclature
a ) specific interfacial area (m2 m-3)
A ) jacket area (m2)
Ai ) frequency factor for the ith rate constants (kg mol-1 h-1)
c, Csi ) concentration of polymer in solution (kg/100 kg, g cm-3)
[Ci] ) concentration of -caprolactam (1) and cyclic dimer (2) in
liquid phase (mol (kg of mixture)-1)
v
Cp,i ) specific heat of pure i in vapor phase (kJ kg-1 K-1)
1
Cp,mix
) specific heat of liquid reaction mixture (kJ kg-1 K-1)
ds ) diameter of stirrer (m)
Di ) diffusivity of component i; i ) m (monomer), w (water) (m2
h-1)
Dr ) diameter of reactor (m)
DP ) degree of polymerization of polymer product
Ei ) activation energy of ith reaction (J mol-1)
F ) mass of liquid in reactor at time t (kg)
hi ) heat transfer coefficient of liquid (kJ m-2 h-1 K-1)
Hi ) enthalpy change for ith reaction (J mol-1)
k ) thermal conductivity of reaction mass (kJ m-1 h-1 K-1)
ki ) rate constants for ith reaction (kg mol-1 h-1)
(kl,ia)j ) liquid-phase mass transfer coefficient of component i;
i ) m (monomer), w (water); for desorption from j; j ) f (free
surface); b (bubble surface) (m h-1)
Ki ) equilibrium constants for the ith reaction
mI ) ratio of polymer free volume to segment free volume
[Mv] ) concentration of -caprolactam in vapor phase (mol m-3)
Mn ) number-average molecular weight
Mw ) weight-average molecular weight
n ) rate of rotation of stirrer (rev min-1)
Nj-i ) normality of the ith solution with the jth solute
[Nv] ) concentration of nitrogen or argon in the vapor phase
(mol m-3)
NRe ) Reynolds number
NSc ) Schmidt number
NSh ) Sherwood number
P ) total pressure (kPa)
Pisat ) vapor pressure of component i (kPa)
Q ) polydispersity index

ri ) net forward rate for ith reaction (mol kg-1 h-1)

ri, I ) number of segments of i per polymeric species I
R ) universal gas constant (kPa m3 mol-1 K-1 or J mol-1 K-1)
Rvm ) rate of evaporation of -caprolactam (mol h-1)
Rvw ) rate of evaporation of water (mol h-1)
[Si] ) concentration of linear oligomers in liquid (mol kg-1)
Si ) entropy change for ith reaction (J mol-1 K-1)
t ) time (h)
tf ) total (final) reaction time (h)
T ) temperature (K)
Tr ) reference temperature () 473.15 K)
Vg ) volume of the vapor space (m3)
VT ) rate of the vapor escape from the reactor (mol h-1)
Xi ) segment fraction of species i at time t
{}
Xm
) monomer conversion
grav
Xm
) monomer conversion obtained using gravimetry
GC
Xm
) monomer conversion obtained using gas chromatography
xi ) mole fraction of species i at time t
[W] ) water concentration in liquid (mol/(kg of mixture))
[Wv] ) water concentration in vapor (mol m-3)
w/w ) mass fraction
Greek Symbols
R ) nonrandomness factor (poly-NRTL/NRF model)
i ) activity coefficient of i
) viscosity of liquid mixture (Pa s or poise; 1 poise ) 10-1
Pa s)
[] ) intrinsic viscosity of -caprolactam-nylon-6 mixture (100
(kg of mixture)/(kg of polymer))
ij ) poly-NRTL/NRF binary interaction parameter for components
i and j
i ) total moles of monomer (i ) 1), water (i ) 2), or both
(i ) 3) vaporized till time t (mol)
i ) moments of the Sn distribution (i ) 0, 1, 2)
n ) number-average chain length ( 1/0)
F ) density of the liquid mixture (kg m-3)
i ) volume fraction of species i
) relative supersaturation
c ) critical value of the relative supersaturation at which the highbubbling regime starts
) enhancement factor for the volumetric liquid-phase mass
transfer coefficient for the free liquid surface due to bubbling
b ) supersaturation in the liquid phase that determines the start
of bubbly desorption (when b > P) (kPa)
Subscripts/Superscripts
b ) bubble/bubbly
expt ) experimental value
f ) free surface
J ) jacket
l ) liquid
m ) monomer
o ) feed conditions
q ) quiescent
sim ) simulation values
v ) vapor
w ) water
*) interfacial
Note: Additional details can be found in refs 12, 17, and 25.

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ReceiVed for reView February 19, 2008

ReVised manuscript receiVed April 29, 2008
Accepted April 30, 2008
IE800287D