Chemical Engineering Science 107 (2014) 256–265

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Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Process parameter optimization through Design of Experiments in

synthesis of high cis-polybutadiene rubber
Madhuchhanda Maiti a,n, Vivek K. Srivastava a, Satish Shewale a, Raksh Vir Jasra a,
Ankur Chavda b, Siddharth Modi b
a
Reliance Technology Group, Vadodara Manufacturing Division, Reliance Industries Ltd., Vadodara 391346, Gujarat, India
b
Dharmsinh Desai University, Nadiad 387001, Gujarat, India

H I G H L I G H T S

The polymerization of butadiene was investigated with a neodymium-based catalyst system using DOE.

The optimum conditions for the polymerization were determined using developed models.

The developed model equations for active catalyst phase and reaction phase were validated.

The developed models can turn out to be very effective to predict the response for given set of operating conditions.

art ic l e i nf o a b s t r a c t

Article history: The neodymium octanoate (Nd), diethylaluminum chloride (DEAC) and triethylaluminum (TEAL)-based
Received 27 June 2013 catalyst system was studied for polymerization of 1,3-butadiene (BD). The present paper deals with the
Received in revised form identification of linear, square and interaction effects of the process parameters on conversion, molecular
27 November 2013
weight and microstructure of the polybutadiene rubber and consequently the optimization of poly-
Accepted 3 December 2013
Available online 18 December 2013
merization process using statistical tool, Design of Experiments. The process comprises of two steps:
(1) active catalyst formulation and (2) polymerization of BD. Both steps were optimized sequentially
Keywords: using Box–Behnken design (BBD) and each BBD has three independent variables. In both designs and
Design of Experiments models, the proposed correlations represent the experimental data adequately for response variables viz.
Polymerization
conversion, molecular weight and cis-content. Optimum catalyst formulation was observed to be BD/Nd,
1,3-Butadiene
DEAC/Nd and TEAL/Nd molar ratio of 902.88, 1.74 and 27.51, respectively. Optimum polymerization
Neodymium
cis-Polybutadiene rubber conditions were monomer concentration 22%, reaction time 3.3 h and reaction temperature 42 1C for the
said catalyst system.
& 2013 Elsevier Ltd. All rights reserved.

1. Introduction particular interest is that it provides an opportunity to achieve

Polybutadiene rubber (BR) is a resultant polymerization
product of 1,3-butadiene (BD) monomer in the presence of
Ziegler–Natta catalyst system. The global consumption and pro-
duction of BR were approximately around 2.8 million metric tons
per year in 2010, and it is forecasted to increase around 4.0% per
year from 2010 to 2015 (Singh et al., 2012). Among the annual
global production, largest portion is applied to the tire industries.
From catalyst viewpoint, neodymium (Nd)-based catalyst
systems have shown great potential and prospects for BD poly-
merization process (Friebe et al., 2003). The reason for this
n
Corresponding author. Tel.: þ 91 265 6696000; fax: þ 91 265 6693934.
E-mail addresses: madhuchhanda.maiti@ril.com,
madhu.c.maiti@gmail.com (M. Maiti).
Z98% of cis-content in the rubber which is higher than any other
catalyst system such as Ti, Co and Ni (Annunziata et al., 2011; Ricci
et al., 2010; Singh et al., 2010, 2012; Srivastava et al., 2011). Nd
based polybutadiene rubber has most linear chain structure (no
branching) with the best tensile and hysteresis (low heat build-up)
properties. It also shows better abrasion resistance and higher
resilience which are very favorable properties for tire, golf-ball as
well as high impact-polystyrene (HIPS) based applications (Friebe
et al., 2006).
The structural properties of the rubber have vital significance in
the product manufacturing process as they determine the physical
properties and the processability of the obtained rubber. On the
other hand, variation in catalyst system and in process conditions
results significant change in structural properties of rubber. There-
fore, the catalyst system and process conditions must be optimized
to achieve predetermined quality specification of the rubber. This

0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.12.002
 M. Maiti et al. / Chemical Engineering Science 107 (2014) 256–265
is especially true for multivariable and highly non-linear processes
such as polymerization, where interaction effects are present
(Delfa et al., 2009). Conventionally, most of the optimization
studies during the development of a process involve variation of
one factor at a time, holding all other factors constant. However, it
requires more number of experimental runs and consequently
increases the time-line and expenses of the project. Therefore, in
such situations the use of Design of Experiments (DOE) has gained
popularity as it evaluates all process variables at the same time,
and helps in quantifying linear, square and interactive effects of
the test variables (Box and Draper, 1987; Mason et al., 1989).
Some efforts have been attempted for carrying out DOE in the
field of polymerization process. Early in 1981, Daroux et al. (1981)
applied a factorial Design of Experiments in the bulk polymeriza-
tion of styrene to identify the significant as well as interaction
effects of process parameters on conversion and polydispersity. Ho
et al. (1986) used statistical experimental design for butadiene
polymerization with CoCl2  4Py/Et2AlCl/H2O system to identify the
individual and joint effects of polymerization variables on rate
constants, molecular weight, and polydispersity. Robert and Oscar
(1989) applied statistical method to evaluate the effect of EPDM-
polypropylene polymerization variables on properties of olefinic
thermoplastic elastomers.
Koch et al. (1991) applied a mathematical approach of Design of
Experiment and statistical analysis to the ethylene polymerization.
Scott et al. (1993) studied DOE to investigate an ethylene-vinyl
acetate semi-batch emulsion copolymerization for further optimi-
zation of the process conditions. The authors also discussed the
effects of the process variables on the rate of polymerization,
copolymer composition, particle size and number, molecular
weight and gel content. Later, the effect of operational parameters
on emulsion polymerization of a vinyl-acrylic copolymer was
investigated by Limon et al. using Taguchi method (Limon and
Hernandez, 1996). Carlos et al. (1999) applied a statistical method
to obtain thermally stable polyether resins. Pross et al. (1993)
developed a mathematical model for polymerization of 1,3-buta-
diene using neodymium versatate, ethylaluminium sesquichloride
and triisobutylaluminium system at 45 1C which was able to
describe the kinetics of polymerization at different catalyst ratios,
assuming that the polymerization process was governed by a
‘living’ mechanism. Later Iovu et al. (1999) studied the mechanism
of the polymerization processes of isoprene and butadiene with
the binary neodymium-catalyst system using two mathematical
models: one which takes into account a monomolecular termina-
tion and the other which considers that no termination reactions
occur during the polymerization process. In this context, it is
worth to mention that the butadiene polymerization is highly
complex in nature and reaction mechanism varies a lot with the type
of catalyst, solvent and polymerization conditions, as observed in these
two studies.
Later, Cheng (2002) applied a 23 factorial experimental design
to study the main, two-factor interaction and three-factor inter-
action effects of polymerization time, concentration of HNO3 and
APS/AN molar ratio on the yield of polyaniline powder. Forte et al.
(2003) statistically analyzed the effect of different titanium molar
ratios on the catalytic activity and polymer characteristics of
ethylene/1-butene copolymerization through response surface
methods. Valea et al. (2004) applied Taguchi method to develop
a model for emulsion polymerization and later it was applied to
styrene polymerization to improve the quality of polystyrene in
semi-continuous processes.
Musavi et al. (2005) studied a slurry polymerization of ethylene
in the presence of antifouling fatty amine by a Ziegler–Natta
catalyst through 23 full factorial experimental design. Later,
Silvares et al. (2006) applied DOE to investigate the batch poly-
merization of methyl methacrylate in a tubular photochemical
257
reactor to optimize polydispersity and conversion. Mahdi and
Amir (2009) applied experimental design in batch emulsion
polymerization of vinyl chloride to investigate the effects of
operating variables on particle size and particle size distribution.
Pontes et al. (2011) used the technique of experimental design on
ethylene polymerization process model in order to map the
feasible optimal region as preliminary information for process
optimization.
However, even after two decades of Nd-based technology came
into focus, no study has been reported for statistical DOE of
polymerization process of 1,3-butadiene to produce polybutadiene
rubber using Nd-based catalyst system. The lack of such an
interesting study has motivated us to investigate Nd-based buta-
diene polymerization process through advanced approach of DOE
to explore significant as well as interaction effect of the process
parameters. Such studies would provide an in-depth analysis to
map the most feasible optimal region of process and future
predictions of response variable using model equation. A statistical
(‘black box’) DOE approach has been chosen here as there is no
standard mathematical model available for predicting butadiene
polymerization using Nd-based ternary catalyst system. However,
this study may lead to the use of even simplified model for the
optimal Design of Experiments (model-based Design of Experi-
ments; Franceschini and Macchietto, 2008; Vlachos et al., 2006) in
future.
2. Experimental
2.1. Materials
Neodymium (III) 2-ethylhexanoate (Nd) of 15% (w/w) in hep-
tane was procured from Strem Chemicals, USA. 1,3-Butadiene (BD),
triethylaluminum (TEAL, of 8% (w/w) solution), diethylaluminum
chloride (DEAC, 12.5% (w/w) solution), phosphate of polyoxyethylene
alkyl phenyl ether (PPA), and 2,6-di-tert-butyl-4-methylphenol
(DTBPC) were obtained from Reliance Industries Limited (RIL), Vado-
dara. Cyclohexane and Carbon disulfide (CS2, spectroscopic grade)
were obtained from Labort Fine Chem Pvt. Ltd., India. The mixture of
reactants consists of proportional amount of BD and cyclohexane
solvent, will be hereafter called ‘feed’.
2.2. Polymerization
The 1L jacketed glass reactor (BUCHI AG USTER, Switzerland)
was used for polymerization. The reactor was initially dried out
with heat-gun at 200 1C for 20–25 min. The reactor was cooled
down to 25 1C with the help of constant temperature bath under
nitrogen flushing to ensure complete removal of moisture and air
from the reactor. Once the temperature reached at 25 1C, the
catalyst components (Nd:DEAC:TEAL) were charged according to
stoichiometric requirement under the nitrogen atmosphere, and
allow to age for 30 min. Then the earlier prepared feed solution
containing calculated amount of butadiene was charged to the
reactor and temperature was raised to desired value. The reaction
mixture was continuously stirred during polymerization in order
to prevent monomer diffusion limitations (Wilson, 1996). The
reaction was carried out for two hour. The polymerization was
terminated by venting off any residual monomer and charging
calculated amount of polyoxyethylene alkyl phenyl ether (PPA)
to kill the catalyst activity. Finally the mass was coagulated with
1% (w/v) 2,6-di-tert-butyl-4-methylphenol (DTBPC)/methanol
mixture. The coagulated rubber was taken out from the solvent
and dried overnight in a hood and finally in a vacuum oven at
room temperature until constant weight.
258 M. Maiti et al. / Chemical Engineering Science 107 (2014) 256–265

2.3. Characterization optimum catalyst formulation and optimum reaction conditions

Conversion of monomer was calculated from the weight of
obtained rubber compared to the initial weight of the charged
monomer.
Cis, trans and vinyl-contents were determined by FTIR spectro-
photometer (NICOLET 6700, USA) using frequencies at 740, 912
and 965 cm  1, respectively, by dissolving the rubber sample in
carbon disulfide (75 mg in 10 ml of carbon disulfide), according to
the literature reported Morero method (Ciampelli et al., 1963). The
results of FTIR were also verified by 13C NMR spectroscopy. 13C
NMR was done using Bruker – 400 MHz AVANCE – III.
The viscosity average molecular weight was calculated from the
intrinsic viscosity ½η by applying the Mark–Houwink equation:
½η ¼ k  ðM V Þα
where ½η is the intrinsic viscosity, M V is Molecular weight, ‘k’ and
‘α’ are constants for a solvent system. ‘k’ ¼0.000305 and ‘α’ ¼0.725
for toluene at 25 1C. Sample was prepared by taking 0.125 g of
rubber in 25 ml of toluene.
3. Experimental design for 1,3-butadiene polymerization
Polymerization of 1,3-butadiene with Nd-based catalyst system
comprises two sequential sub-processes viz. (1) Synthesis of active
catalyst formulation and (2) polymerization of 1,3-butadiene or
reaction phase, as objective of the present work was to get
Table 1
Independent variables and their levels for active catalyst formulation.
Independent variables Symbol Low level Center point
BD/Nd molar ratio A 500 800
DEAC/Nd molar ratio B 1 2 3
TEAL/Nd molar ratio C 20 45
for polymerization. In each sub-process there were three inde-
pendent variables, which were selected based on our preliminary
study (Maiti et al., 2011). Since, objective of the work was
optimization; it was decided to use response surface methodology
(RSM), which is typically used to determine optimum operating
conditions for the system or to determine a region of factor space
in which operating requirements are satisfied (Montgomery,
2009). Box–Behnken design (BBD), central composite design
(CCD) full and CCD half for six independent variables consists of
54, 90 and 54 experimental runs, respectively; this makes DOE
comprehensive and time consuming. Hence, based on the guide-
lines for designing experiments (Montgomery, 2009) it was
decided to use sequential approach employing a series of two
DOEs i.e. DOE to find optimum catalyst formulation followed by
ð1Þ
DOE to find optimum reaction conditions for polymerization of
butadiene using optimum catalyst formulation. BBD was specifi-
cally selected since it requires fewer runs than a CCD in case of
three independent variables. BBD has been popularly used for the
second-order response surface model. It is formed by combining
two-level factorial designs with incomplete block designs in a
special manner. BBD is a spherical design, with all points lying on a
sphere of radius √2 and does not contain any points at the
vertices of the cubic region created by the upper and lower levels
for each variable. BBD is rotatable (or nearly rotatable) and
requires 3 levels of each factor (Montgomery, 2009). BBD is also
an orthogonal design. BBD provides information of direct effects,
interaction effects and curvilinear effects of independent variables.
In the Box–Behnken design for preparation of active catalyst
formulation, following three independent variables were set at
low and high level with one center point (Table 1):
High level
1. Catalyst concentration i.e. BD/Nd molar ratio,
1100 2. Halide donor concentration i.e. DEAC/Nd molar ratio, and
70
3. Cocatalyst concentration i.e. TEAL/Nd molar ratio.

Other independent variables were kept constant; e.g., ageing

Table 2
temperature¼25 1C, and ageing time¼30 min, monomer con-
Independent variables and their levels for reaction phase.
centration¼12%, reaction time¼2 h, and reaction temperature¼60 1C.
Independent variables Symbol Low level Center point High level The levels of the independent variable shown in Table 1 were chosen
based on preliminary study (Maiti et al., 2011).
Monomer concentration (wt.%) X 12 17 22 In the Box–Behnken design for reaction phase three indepen-
Reaction time (h) Y 2 3 4
Reaction temperature (1C) Z 40 55 70
dent variables viz. monomer concentration, reaction time and
reaction temperature were set at low and high levels with one

Table 3
Active catalyst formulation: DOE and observed dependent variables.

Serial no. Independent variables Response variables

BD/Nd ratio (A) DEAC/Nd ratio (B) TEAL/Nd ratio (C) Conversion (%) Molecular wt. (g/mol) Cis-content (%)

DOE 1/1 800 2 45 80.0 309,116 86

DOE 2/1 500 2 20 59.2 353,076 85
DOE 3/1 500 1 45 15.6 271,601 81
DOE 4/1 800 2 45 74.6 319,549 86
DOE 5/1a 500 3 45 n n n
DOE 6/1 1100 1 45 67.0 436,887 88
DOE 7/1 1100 3 45 1.1 134,907 91
DOE 8/1 1100 2 20 26.1 281,104 91
DOE 9/1 800 1 20 48.4 357,179 90
DOE 10/1 500 2 70 5.9 242,548 85
DOE 11/1 1100 2 70 33.3 256,475 89
DOE 12/1 800 2 45 81.2 309,994 86
DOE 13/1 800 3 70 0.1 468,235 92
DOE 14/1 800 1 70 35.2 190,984 89
DOE 15/1 800 3 20 3.4 550,082 92

a
Characterization of sample could not be performed due to very low yield of polymer in reaction mixture.
 M. Maiti et al. / Chemical Engineering Science 107 (2014) 256–265 259

center point (Table 2). These experiments were performed with P-values were used as a tool to understand significance of
optimum active catalyst formulation, which was determined from linear, square and interaction terms in the model. Lower the P-
DOE for active catalyst formulation. value, more is the significance of the term. Whenever the P-value
Dependent variables or response for both designs of experi- is lower than 0.05, an independent variable has significant
ments were % conversion of monomer (1,3-butadiene), molecular influence on dependent variables viz. conversion, average mole-
weight of polymer and % cis-content of polymer. Both experimen- cular weight and cis-content.
tal designs with observed response variables are given later in the It can be seen from Table 4 that A, B, A2, B2, C2, AB and AC
text. Statistical software MINITABs 15 (Minitab Inc., USA) was significantly affect % conversion of monomer; A, B2 and AB
used for creating the Design of Experiments (i.e. BBD), fitting significantly affect molecular weight of polymer; and A, C, A2, B2
response variables in quadratic model, ANOVA of proposed models and C2 have significant effect on cis-content of the polymer. Table 4
and multi-response optimization to obtain optimum independent clearly shows that term A has significant effect on all responses;
variables. however, B has significant effect on % conversion and C has
significant effect on cis-content of the polymer. It can be also seen
that interaction AB is significant for % conversion and molecular
4. Results and discussion weight; interaction AC is significant for % conversion; whereas
interaction between B and C is not significant for any response
4.1. Active catalyst formulation variable. The R-square (R2) value indicates the proportion of the
variability in the response explained by the regression equation.
4.1.1. Statistical analysis The estimated R2 value for each response; conversion (97.21%),
The Box–Behnken experimental design of active catalyst for-
mulation phase with experimentally obtained dependent (or
Table 5
response) variables such as conversion (%), average molecular ANOVA for proposed quadratic model for catalyst formulation.
weight (g/mol) and cis-content (%) is reported in Table 3. The
error associated with experiments was incorporated by three Source DF Seq SS Adj SS Adj MS F P
replicated experimental runs at center points (Runs 1, 4 and 12);
Response: % conversion
this is unexplained variance in the experimentation or within- Regression 9 11,733.4 11,733.4 1303.71 15.46 0.009
group variability. This variance must be as low as possible because Linear 3 2814.9 4031.84 1343.95 15.93 0.011
it will significantly affect experimentation reliability and hence Square 3 7178.3 6366.11 2122.04 25.16 0.005
further estimated mathematical model. Pure error obtained by Interaction 3 1740.2 1740.16 580.05 6.88 0.047
Residual error 4 337.4 337.37 84.34
ANOVA technique is the error in replicated experiments.
Lack-of-fit 2 312.6 312.65 156.32 12.65 0.073
Experimental data was fitted into quadratic (second order) Pure error 2 24.7 24.72 12.36
model. Regression coefficient for the quadratic model and sig- Total 13 12,070.8
nificance probability (P-value) of each factor in the model is given Response: molecular weight
in Table 4. Full quadratic models for % conversion (% C), molecular Regression 9 1.00E11 1.00E11 1.11E10 30.49 0.002
weight (MW) and % cis-content (% Cis) for catalyst formulation are Linear 3 1.47E10 1.01E10 3.37E09 9.23 0.029
as follows; Square 3 4.58E10 5.31E10 1.77E10 48.56 0.001
Interaction 3 3.95E10 3.95E10 1.32E10 36.13 0.002
% C ¼  257:38 þ 0:413A þ 151:6B þ 1:77C  2:27  10  4 A2 Residual error 4 1.46E09 1.46E09 3.65E08
Lack-of-fit 2 1.39E09 1.39E09 6.96E08 20.77 0.046
 29:976B2  0:043C 2  0:067AB þ 2:015  10  3 AC þ 0:1BC Pure error 2 6,697,233 66,972,133 33,486,066
ð2Þ Total 13 1.02E11

Response: cis-content
MW ¼  58765:3 þ1012:2A  28600:5B  496:5 C Regression 9 139.30 139.30 15.48 26.8 0.003
2 2
0:139A þ 123861:8B2 þ 11:46C  466:86AB Linear 3 82.46 36.9 12.30 21.31 0.006
Square 3 54.67 50.32 16.77 29.05 0.004
0:371AC 311:65BC ð3Þ
Interaction 3 2.17 2.17 0.72 1.25 0.402
Residual error 4 2.31 2.31 0.577
% Cis ¼ 76:256 þ4:39  10  2 A 3:75B 0:397C Lack-of-fit 2 2.16 2.16 1.079 14.27 0.065
 1:76  10  5 A2 þ 1:626B2 þ 4:97  10  4 C 2 Pure error 2 0.151 0.15 0.075
Total 13 141.61
 1:39  10  3 AB  8:93  10  5 AC þ 3:5  10  3 BC ð4Þ

Table 4
Proposed quadratic models for conversion, molecular weight and cis-content for catalyst formulation.

Term Conversion (%) Molecular weight (g/mol) Cis-content (%)

Coefficient P value* Coefficient P value* Coefficient P value*

Constant  257.38 0.01 (S)  58,765.3 0.641 (NS) 76.256 0 (S)

A 0.413 0.013 (S) 1012.2 0.007 (S) 4.39E-02 0.005 (S)
B 151.6 0.004 (S)  28,600.5 0.611 (NS)  3.75 0.144 (NS)
C 1.77 0.148 (NS)  496.5 0.821 (NS)  0.397 0.008 (S)
A2  2.27E 04 0.018 (S)  0.139 0.320 (NS)  1.76E-05 0.023 (S)
B2  29.796 0.005 (S) 123,861.8 0 (S) 1.626 0.021 (S)
C2  0.043 0.007 (S) 11.46 0.551 (NS) 4.97E-03 0.002 (S)
AB  0.067 0.037 (S)  466.86 0 (S)  1.39E-03 0.482 (NS)
AC 2.015E  03 0.03 (S)  0.371 0.785 (NS)  8.93E-05 0.153 (NS)
BC 0.100 0.617 (NS)  311.65 0.460 (NS) 3.5E-03 0.829 (NS)
R2 97.21 98.56 98.37

n
Significance of the term is mentioned in bracket. ‘S’, significant; ‘NS’, non-significant.
260 M. Maiti et al. / Chemical Engineering Science 107 (2014) 256–265

molecular weight (98.56%) and cis-content (98.35%) signify that

experimental data are well explained by developed models.
ANOVA is a statistical technique that subdivides the total 350000
600000
variation in a set of data into component parts associated with

MW
specific sources of variation and it was used to check significance 300000

MW
400000
and fitness of the proposed model. ANOVA of proposed quadratic 3
250000 60
200000 2 Nd

Nd
model for all response variables is given in Table 5. Source / 40
AC

/
500 750 500 750

AL
1 20
indicates the source of variation, either from the factor, the 1000 DE 1000

TE
B D/N B D/Nd
d
interaction, or the error. The total is a sum of all the sources. DF
is ‘degrees of freedom’ from each source. SS is the ‘sum of squares’
between groups (factor) and the sum of squares within groups
(error). MS is ‘mean squares’ that are found by dividing the sum of Hold Values
500000
squares (SS) by the degrees of freedom (DF). F is the ratio of BD/Nd ratio (c) 800
DEAC/Nd ratio (b) 2

MW
explained variance to unexplained variance or ratio of between- 400000
group variability to within-group variability. F is calculated by 60 TEAL/Nd ratio(a) 45
300000

Nd
dividing the factor MS by the error MS. F value of regression is 40

/
1

AL
2 20
compared with critical F value, which is obtained from table of 3

TE
DEAC
/Nd
F given in the book by Montgomery (2009) to check whether
variation in response is well explained by the regression model or Fig. 2. Surface plots for molecular weight (MW).
not. F value for regression of % conversion, molecular weight and
cis-content was 15.46, 30.50 and 26.80, respectively, which are
greater than critical F0.05,9,4 (6.00). In F0.05,9,4, 0.05 is the P-value to
check significance of model, 9 is the degrees of freedom of 90
90
regression and 4 is the degrees of freedom of residual error. The

% Cis
87

% Cis
large value of F indicates that most of the variation in the response 85
can be explained by the regression model equation. High F value of 84
3
d 60
regression for all response variables indicates that models are 80 2 /N 81

Nd
C 40
500 1 EA 500

/
AL
750 1000 750 20
significant. A P-value lower than 0.05 indicates that model is D BD/N 1000

TE
B D/Nd d
significant, whereas values higher than 0.1 indicates that model is
non-significant. P-value of model for all response variables lower
than 0.05 indicates that all proposed models are statistically
significant. High lack of fit F value implies that lack of fit is not Hold Values
92.5
significant relative to pure error.
90.0
BD/Nd ratio (c) 800
% Cis

DEAC/Nd ratio (b) 2

87.5
4.1.2. Effect of independent variables 60 TEAL/Nd ratio(a)45
85.0
Nd

40
Figs. 1–3 illustrate the surface plots, representing a number of 1
/
AL

20
DEA 2 3
combinations of two test variables with the other variable main-
TE

C /N
d
tained at fixed level (hold value), for % conversion, molecular
weight and cis-content, respectively. It can be seen from Fig. 1 Fig. 3. Surface plots for cis-content (% Cis).

that the interaction effect of BD/Nd ratio with DEAC/Nd ratio and
TEAL/Nd ratio is more prominent than the linear effect of BD/Nd place which finally reduces the activity of catalyst (Friebe et al.,
ratio. Initially with increasing DEAC/Nd ratio the catalytic activity 2006). The cocatalyst to catalyst ratio (TEAL/Nd ratio) also plays an
increases due to contribution of halide donor, which results into important role in polymerization. In activation reaction alkyl
higher conversion up to certain molar ratio. However, beyond a groups are transferred from alkyl aluminum to the Nd centers
specific molar ratio, the formation of insoluble salt of NdCl3 takes and enhances the activity of catalyst up to certain molar ratio.
Furthermore, during the reaction alkyl aluminums act as Lewis
acids, that abstract halides or alkyl groups from Nd to create free
coordination sites on Nd and thus enhance the activity of catalyst
75 75 (Friebe et al., 2006).
50 50 The reaction becomes faster at low BD/Nd ratio, which makes
%C %C the product less selective in nature and results into lower cis-
25 25
0
3
60 content material. With increasing DEAC/Nd molar ratio, the
d

0
d

2
N

40 coordination between chloride and Nd 4f orbitals are induced,

/N
C/

500 750 500 750

AL
EA

1 1000 20
1000 and the cis coordination of dienes is enhanced. The similar
D

BD/N
TE

BD/N
d d
phenomenon was also observed by Evans et al. (2001).
Fig. 4 shows the overlaid contour plots, which is being used to find
out the feasible region for the process. The area in white color points
Hold Values out the feasible region of the polymerization for the desired output
75
BD/Nd ratio (c) 800 response (e.g., conversion¼65–75%; molecular weight¼ 2.5–3.5  105;
50
%C DEAC/Nd ratio(b) 2 cis-content¼ 88–90%).
25
TEAL/Nd ratio(a) 45
0 60
d
/N

40
1
AL

2 20 4.1.3. Optimization
DE AC 3
TE

/Nd
Response optimizer helps to identify the combination of input
Fig. 1. Surface plots for conversion (% C). variable settings that jointly optimize a single response or a set of
 M. Maiti et al. / Chemical Engineering Science 107 (2014) 256–265 261

Fig. 4. Overlaid contour plots for conversion (% C), molecular weight (MW) and cis-content (% Cis).

Table 6
Predicted versus validation results with optimum catalyst formulation (BD/Nd
molar ratio ¼ 902.88, DEAC/Nd molar ratio ¼ 1.74 and TEAL/Nd molar ratio ¼
27.51).

Response factors Predicted results Validation resultsa

Run 1 Run 2

Conversion (%) 70 85 83
Molecular weight (g/mol) 306,100 321,913 315,865
Cis-content (%) 88.6 89 89

a
Other reaction conditions: ageing temperature ¼ 25 1C and ageing time ¼
30 min, monomer concentration ¼ 12%, reaction time ¼ 2 h, and reaction
temperature ¼ 60 1C.

responses. Joint optimization or multi response optimization must

Fig. 5. Optimization plots for conversion, molecular weight and cis-content.
(D: composite desirability, d: individual desirability, Targ.: target, high and low
indicates high and low levels of independent variables in DoE, Cur: position of
cursor, y: value of response variables at cursor or optimal independent variables).
satisfy the requirements for all the responses in the set, which is
measured by the composite desirability. The response optimizer
tool was used to find out the best optimum conditions for active
catalyst formulation phase. The optimization is accomplished by:
(1) obtaining the individual desirability (d) for each response,
(2) obtaining the combined or composite desirability (D), which is
the weighted geometric mean of the individual desirabilities for
the responses, and (3) employing a reduced gradient algorithm
with multiple starting points that maximizes the composite
desirability to determine the numerical optimal solution (optimal
independent variables).
As shown in Fig. 5, the optimum conditions for active catalyst
formulation are; BD/Nd molar ratio¼902.88, DEAC/Nd molar
262 M. Maiti et al. / Chemical Engineering Science 107 (2014) 256–265

ratio ¼1.74 and TEAL/Nd molar ratio¼27.51, with the predicted
responses: % conversion¼70, molecular weight ¼306,100, and cis-
content¼88.6%. Composite desirability varies from zero to one.
One represents the ideal case; zero indicates that one or more
responses are outside their acceptable limits. The composite
desirability (D) for all the response factors was 0.85607, which is
fairly closer to ideal one and hence, well acceptable.
Two validation experiments at optimum catalyst formulation
were performed to verify the reliability of model equation, and
consistency of analytical results. The predicted results for average
molecular weight and cis-content by model equation and the
results obtained from validation experiments are similar and
falling within the acceptable range (Table 6) which confirms the
statistical effectiveness of the developed model. In the polymer-
ization of 1,3-butadiene, the cis-content and molecular weight are
the most important properties which has to be monitored. As
these two properties were accurately predicted from the model,
optimal design approach was not checked.  20% variation in
conversion can be observed in predicted and experimental meth-
ods. Usually, in lab-scale experimentation with commercial-grade
chemicals, such variation in conversion is observed and accepta-
ble.  20% variation in viscosity average molecular weight of tire-
grade high molecular weight polybutadiene is also acceptable. Any
ingress of moisture in alkyl aluminums can cause this variation. As
these are of commercial grade and collected from manufacturing
plant site and then used in laboratory, such variations can be
observed.
4.2. Reaction phase
4.2.1. Statistical analysis
Box–Behnken experimental design of reaction phase with
experimentally obtained dependent (or response) variables; con-
version (%), molecular weight (g/mol) and cis-content (%) is
reported in Table 7.
Experimental data was fitted into quadratic (second order)
model; regression coefficient for the quadratic model and P-value
of each term in the model is given in Table 8. Full quadratic models
for % conversion (% C), molecular weight (MW) and % cis-content
(% Cis) for reaction phase are as follows;
% C ¼  431:8 þ 7:06X þ 80:24Y þ 15:28Z  4:77  10  2 X 2
 6:27Y 2 0:592Z 2  0:711XY þ9:03  10  2 XZ þ 0:551ZY
ð5Þ
MW ¼ 1794761:4  45288:85X þ396309:37Y
 40531:19Z þ 349:32X 2  63049:41Y 2 þ 531:63Z 2
 928:02XY þ22:46XZ þ1914:98ZY ð6Þ
% Cis ¼ 111:49  0:193X þ 5:15Y  1:75Z
þ 3:12  10  3 X 2  1:22Y 2 þ 8:29  10  2 Z 2
þ 2:53  10  2 XY 2:70  10  2 XZ þ 9:0  10  3 ZY ð7Þ
2 2 2
It can be seen from Table 8 that X, Y, Z, X , Y , Z , XY and XZ
significantly affect % conversion of monomer; X, X2 and Y2

Table 7
Reaction phase: DOE and observed dependent variables.

Serial no. Independent variables Response variables

Reaction temp. (1C) (X) Reaction time (h) (Y) Monomer conc. (%) (Z) Conversion (%) Molecular wt. (g/mol) Cis-content (%)

DOE 1/2 40 2 17 22 574,392 93

DOE 2/2 70 3 12 56 451,593 93
DOE 3/2 55 3 17 79 381,649 88
DOE 4/2 70 4 17 84 253,285 84
DOE 5/2 55 4 22 82 327,814 87
DOE 6/2 55 4 12 63 405,989 89
DOE 7/2 40 3 22 41 598,287 93
DOE 8/2 55 2 12 43 416,240 91
DOE 9/2 55 2 22 50 299,765 89
DOE 10/2 40 4 17 69 591,440 91
DOE 11/2 55 3 17 80 479,156 89
DOE 12/2 40 3 12 32 734,687 95
DOE 13/2 55 3 17 82 415,827 88
DOE 14/2 70 2 17 79 291,918 84
DOE 15/2 70 3 22 91 276,880 83

Table 8
Proposed quadratic models for conversion, molecular weight and cis-content for reaction phase.

Term Conversion (%) Molecular weight (g/mol) Cis-content (%)

* *
Coefficient P value Coefficient P value Coefficient P value*

Constant  431.80 0 (S) 1,794,761.4 0.043 (S) 111.49 0.007

X 7.06 0.001 (S)  45,288.85 0.021 (S)  1.93E  01 0.724 (NS)
Y 80.24 0.001 (S) 396,309.37 0.084 (NS) 5.15 0.493 (NS)
Z 15.28 0.002 (S)  40,531.19 0.349 (NS)  1.75 0.290 (NS)
X2  4.77E 02 0.001 (S) 349.32 0.022 (S) 3.12E  03 0.472 (NS)
Y2  6.27 0.011 (S)  63,049.41 0.046 (S)  1.22 0.233 (NS)
Z2  5.92E  01 0 (S) 531.63 0.602 (NS) 8.29E  02 0.070 (NS)
XY  7.11E  01 0.001 (S)  928.02 0.571 (NS) 2.53E  02 0.680 (NS)
XZ 9.03E  02 0.007 (S) 22.46 0.944 (NS)  2.70E  02 0.067 (NS)
ZY 5.51E  01 0.133 (NS) 1914.98 0.694 (NS) 9.00E  03 0.961 (NS)
R2 99.3 95.9 92.0

n
Significance of the term is mentioned in bracket. ‘S’, significant; ‘NS’, non-significant.
 M. Maiti et al. / Chemical Engineering Science 107 (2014) 256–265 263

Table 9
ANOVA of proposed quadratic model for reaction phase.
750000
Source DF Seq SS Adj SS Adj MS F P 600000
600000

MW
500000

MW
% conversion
400000 450000
Regression 9 6511.91 6511.91 723.546 76.41 0
4 20
Linear 3 4618.71 917.49 305.831 32.3 0.001 300000 300000
3 16 ,%

,h
Square 3 1224.62 1224.62 408.207 43.11 0.001 45 55 45 55 12 nC

Rt
65 2 65
Interaction 3 668.58 668.58 222.861 23.53 0.002 R T , °C R T , °C M
Residual error 5 47.35 47.35 9.469
Lack-of-fit 3 42.81 42.81 14.269 6.29 0.14
Pure error 2 4.54 4.54 2.269
Total 14 6559.26
Hold Values (c)
Reaction Temperature (RT), °C 55
Reaction Time (Rt), h (b)
Molecular weight 500000
3
Regression 9 2.4E11 2.4E11 2.7E10 12.88 0.006
Monomer Concn (MnC), % (a) 17

MW
Linear 3 2.0E11 4.2E10 1.4E10 6.67 0.034 400000
Square 3 4.1E10 4.1E10 1.4E10 6.49 0.036
Interaction 3 1.2E09 1.2E09 3.8E08 0.18 0.904 300000 20
Residual error 5 1.1E10 1.1E10 2.1E09 16 , %
2
3 12 nC
Lack-of-fit 3 8.9E09 8.9E09 3.0E09 3.54 0.228 R t, h 4 M
Pure error 2 1.7E09 1.7E09 8.4E08
Total 14 2.6E11
Fig. 7. Surface plots for molecular weight (MW).
Cis-content
Regression 9 172.911 172.911 19.2123 6.39 0.027
Linear 3 131.441 7.424 2.4746 0.82 0.535
Square 3 24.482 24.482 8.1607 2.71 0.155
Interaction 3 16.988 16.988 5.6627 1.88 0.25 92.5 95
Residual error 5 15.038 15.038 3.0075 90.0

Cis, %
Cis, %
Lack-of-fit 3 13.221 13.221 4.4071 4.85 0.176 90
87.5
Pure error 2 1.816 1.816 0.9081
85.0 4 85
Total 14 187.949 20
3 16

,%
,h
45 55 65 2 45 55 12

nC
Rt
65

M
RT, ° C RT, °C

100 Hold Values (c)

80 Reaction Temperature (RT), °C 55
80 92
(b)
%C

60 Reaction Time (Rt), h 3

%C

60 90
Cis, %

40 Monomer Concn (MnC), % (a) 17

4 40 88
20
20 3 16 20
,%

86
,h

45 55 45 55 16
,%
Rt

nC

65 2 65 12 2 12
nC
M

RT , ° RT , ° 3
C C 4
M

Rt , h

Fig. 8. Surface plots for cis-content (% Cis).

Hold Values (c)
Reaction Temperature (RT), °C55
ANOVA of proposed quadratic model for all response variables
80 Reaction Time (Rt), h (b) 3
is given in Table 9. F value for regression of % conversion,
Monomer Concn (MnC), %17(a)
%C

60 molecular weight and cis-content was 76.41, 12.88 and 6.39,

20 respectively, which are greater than critical F0.05,9,5 (4.77). Large
40
,%

2
16 F value of regression for all response variables indicates that
nC

3 12
R t, h 4 models are significant. P-values are lower than 0.05, which
M

indicates that model is significant.

Fig. 6. Surface plots for conversion (% C).

significantly affect molecular weight of polymer. It is observed that no
term has significant effect on cis-content of the polymer, however, Z2
and XZ has moderate significance on cis-content because correspond-
ing P values are closer to 0.05. It also indicates that active catalyst
formulation mainly decides cis-content of polymer instead of reaction
process parameters. It can be also observed from Table 8 that term
X has significant effect on % conversion and molecular weight of
polymer; term Y has significant effect on % conversion and moderate
effect on molecular weight; term Z has significant effect only on %
conversion. Interaction terms, XY and XZ, significantly affect % conver-
sion. No interaction term had significant effect on molecular weight
and cis-content of polymer. The estimated R2 value for each response;
conversion (99.3%), molecular weight (95.9%) and cis-content (92%)
signify that experimental data are well explained by developed
models.
4.2.2. Effect of independent variables
Figs. 6–8 illustrate the surface plots, representing a number of
combinations of two independent variables with the other vari-
able maintained at fixed level, for % conversion, molecular weight
and cis-content, respectively.
According to Porri and Giarrusso (1989), polymerization tem-
perature has pronounced effect on rate of reaction, which can be
observed in Fig. 6. On increasing the reaction temperature (up to
60 1C) the rate of polymerization reaction increases which finally
results in higher conversion. At temperature 4 60 1C catalyst
deactivation became more prominent and overall catalyst activity
decreased (Pires et al., 2004; Ni et al., 2004). The monomer
concentration and reaction time also show a positive impact on
conversion; higher the monomer concentration and reaction time,
higher the conversion.
264 M. Maiti et al. / Chemical Engineering Science 107 (2014) 256–265
Fig. 9. Overlaid contour plots for conversion, molecular weight and cis-content.
Fig. 10. Optimization plots for conversion, molecular weight and cis-content. (D:
composite desirability, d: individual desirability, Targ.: target, high and low
indicates high and low levels of independent variables in DoE, Cur: position of
cursor, y: value of response variables at cursor or optimal independent variables).
As expected, the molecular weight exhibits highest variability with
reaction temperature. The reduction in molar mass is noticed with
increasing polymerization temperature (Fig. 7). As polymerization
temperature increases the concentration of active sites increases; as
a result low molecular weight polymer is obtained (Friebe et al., 2006).
The microstructure of polybutadiene is mostly controlled by the
linear effect of reaction temperature and monomer concentration.
There is no evidence of any interaction effect on polymer microstruc-
ture. As shown in Fig. 8, the cis-content is decreasing with increasing
polymerization temperature. Reported literature also confirms the
same trend of microstructure with polymerization temperature
(Oehme et al., 1996).
The overlaid contour plot was drawn to find out the feasible region
for the process (Fig. 9). The area in white color shows the feasible
region of process for the desired output response (e.g., conversion¼
45–60%; molecular weight¼4.0–4.5  105; cis-content¼90–94%).
4.2.3. Optimization
The response optimizer tool was used to find out the best reaction
conditions to get desired response. The target value for con-
version¼ 50%, molecular weight¼ 450,000 and cis-content¼95% were
given to the optimizer. As shown in Fig. 10, the optimum conditions for
the reaction phase are; reaction temperature¼42 1C, reaction
time¼ 3 h 20 min. and monomer concentration¼22%. The predicted
response for a new optimum conditions are; conversion¼50.1%,
molecular weight¼523,300, and cis-content¼ 93.4%. The composite
desirability (D) for all the response factors is 0.95578, which is well
acceptable.
The optimum condition was validated thrice to verify the reliability
of model equation and consistency of analytical results. As shown in
 M. Maiti et al. / Chemical Engineering Science 107 (2014) 256–265
Table 10
Predicted versus validation results (optimum reaction conditions: reaction tem-
perature ¼ 42 1C, reaction time ¼ 3 h 20 min. and monomer concentration ¼ 22%).
Response factors Predicted results Validation results*
Run 1 Run 2 Run 3
Conversion (%) 50.1 66 67 69
Molecular weight 523,300 430,626 425,347 446,730
Cis-content (%) 93.4 97 96 96
n
Experiments performed using optimum catalyst formulation: BD/Nd molar
ratio ¼ 902.88, DEAC/Nd molar ratio ¼ 1.74 and TEAL/Nd molar ratio ¼ 27.51.
Other reaction condition: Ageing temperature ¼ 25 1C, and ageing time ¼ 30 min.
Table 10, the validation results and the predicted results of conversion,
molecular weight and cis-content by model equation are similar and
are within the acceptable range. As mentioned in the Section 4.1.3, in
lab-scale experimentation with commercial-grade chemicals, such
variation in conversion is observed and acceptable. 20% variation
in viscosity average molecular weight of tire-grade high molecular
weight polybutadiene is also acceptable.
5. Conclusions
In this study, the polymerization of butadiene (BD) was investi-
gated with a neodymium(III) 2-ethylhexanoate (Nd)/diethylalumi-
num chloride (DEAC)/triethylaluminum (TEAL) based catalyst system
in cyclohexane solvent. The study demonstrated that independent
variables like; BD/Nd, DEAC/Nd and TEAL/Nd molar ratio, monomer
concentration, reaction time and reaction temperature have signifi-
cant linear, squared as well as interaction effect on dependent
variables; such as, conversion, molecular weight and microstructure.
The optimum conditions for the active catalyst formulation using
developed models were BD/Nd molar ratio¼902.88, DEAC/Nd
molar ratio¼1.74 and TEAL/Nd molar ratio¼ 27.51 with predicted
response; conversion¼70%, molecular weight¼ 306,100, and cis-
content¼ 89%. The composite desirability (D) for all the response
factors was 0.85607. Optimum conditions for reaction phase were
monomer concentration¼22%, reaction time¼3 h 20 min. and reac-
tion temperature¼42 1C with predicted response; conversion¼50%,
average molecular weight¼523,300, and cis-content¼93%. The
composite desirability (D) for all the response factors was 0.95578.
The developed model equations for active catalyst phase and reaction
phase were validated thrice. The developed models can turn out to
be very effective to predict the response for given set of operating
conditions, to carry out deeper investigation of process and to map
the feasible region of process.
Acknowledgment
The authors thank Mr. Chirag S. Shah, Ms. Swati G. Trivedi and
Ms. Rashmi Dave for their support. The authors are grateful to
Reliance Industries Ltd. for their consent to publish this work.
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