KINETIC BASED PROCESS MODELING OF THE ISOBUTYLENE

POLYMERIZATION PROCESS
Yongtai Li, Michael Fidell, Paul Anthony, Omar M. Basha and Badie I. Morsi*
Reactor and Process Engineering Laboratory
Department of Chemical and Petroleum Engineering, Unviersity of Pittsburgh, Pittsburgh, PA 15261
* Corresponding author: morsi@pitt.edu

INTRODUCTION

MODEL DEVELOPMENT

Polymers and co-polymers derived from isobutylene (IB) could be produced in a wide range
of molecular weights and could be used in numerous applications. For instance, low
molecular weight liquid polybutenes are used as adhesives, sealants, coatings, lubricants,
and plasticizers, and for the impregnation of electrical cables. Medium molecular weight
polyisobutylene was the first viscosity-index modifiers for lubricants; and high molecular
weight polyisobutylene is used in the production of uncured rubbery compounds and as an
impact additive for thermoplastics. Unfortunately, despite the importance and wide
applications of the isobutylene polymerization process, only its kinetics have been heavily
investigated, whereas efforts towards developing comprehensive reactor models, which can

The final reactor model is expected to predict the reactor performance at various operating
conditions and to optimize the isobutylene polymerization process. It should be
remembered that the overall performance of any reactor is governed by the reaction
kinetics, hydrodynamics and transport parameters. The reaction kinetics are fundamentally
independent of the reactor type and size, however, the hydrodynamics and transport
parameters are strongly affected not only by them, but also by the operating conditions
(Figure 2 (A)).
Thermodynamic
quantities

Stoichiometry

Kinetics

reactor model for the isobutylene polymerization reaction, in continuous agitated reactors.

The final reactor model is expected to predict the reactor performance at various operating
conditions and to optimize the isobutylene polymerization process.

POLYMERIZATION MECHANISM
The carbocationic polymerization of isobutylene Figure 1. (A) AlCl3 (B) TiCl4 (C) Lewis Acid
initiated IB polymerization

and its copolymerization with viable comonomers

is

Figure 2. (A) Interplay among the parameters required for reactor modeling, (B) Algorithm for
reactor modeling

The reactor model equations include material balance for all phases, energy balance and
balance.

These

isobutylene

as highlighted in Table 1.

C6H5C(CH3)2Cl/BCl3
initiating system
1,4-bis(1-chloro-1methylethy1)benzene
(DiCumC1)/BC1
Blocked Bifunctional
Initiators in the Presence of
Di-tert-butylpyridine as a
Proton Trap

Diisobutylene hydrochloride
or triisobutylene
hydrochloride in the presence
of BCl3 and
benzyltriethylammonium
tetrachloroborate
t-Bu-m-DCC/TiCl4/2,4-DMP

Cumyl chloride/TiCl4/2,4dimethylpyridine system

Reference
Norrish and Russell
(1951) [26]
Wichterle et al. (1961)
[27]

= .

= . .

= +

= . ;

5-tert-butyl-1,3-bis(2-chloro2-propyl)benzene (t-Bu-mDCC) or 2-chloro-2,4,4trimethylpentane (TMPCl) in

conjunction with TiCl4
2-chloro-2,4,4trimethylpentane
(TMPCl)/TiCl4 and AlCl3

= .

TiCl4, Me2AlCl, and BCl3

= . ; =

Where is the total concentration of chain

ends

= +
=

Methylaluminum
Bromide Coinitiators
AlBr3

such

as

reactor

investigated. Simulations were carried out

Paulo et al. (2000)

[36]
Bahadur et al. (2000)
[37]

the

overall

X-PIB
X-IB
PIB production (kg/hr)

Schlaad et al. (2000)

[21]

0.5

0.4
0.3

0.45

0.4
0

0.2

reactor

= . .

Chmelir et al. (2007)

[41]

References:
[1] R. Norrish, K. Russell, Transactions of the Faraday Society 48 (1952) 91-98.
[2] O. Wichterle, M. Marek, I. Trekoval, Journal of Polymer Science 53 (1961) 281-287.
[3] R.B. Taylor, F. Williams, Journal of the American Chemical Society 91 (1969) 3728-3732.
[4] S.C. Guhaniyogi, J.P. Kennedy, W.M. Ferry, J. of Macromolecular Science: A 18 (1982) 25-37.
[5] B. Ivan, J.P. Kennedy, Macromolecules 23 (1990) 2880-2885.
[6] M. Gyor, H.-C. Wang, R. Faust, Journal of Macromolecular Science, Part A 29 (1992) 639-653.
.

0.4

0.6
Time (hr)
ko-Initiation (1/hr)
10

0.8

1
100

0.5

0.45

0.9

0.4

0.8

0.35

0.7

0.3

0.6

0.25

0.5

0.2

0.4

0.15

0.3

incorporating mass transfer phenomena

0.1

0.2

0.05

0.1

into the model, moreover optimization

results are shown in Figure 3.

Future model improvements, include the
investigation of impeller design on the
overall performance of the polymerization

Sipos et al.(2003)[22]
De and Faust (2006)
[40]

0.55

0.5

and a sensitivity analysis was conducted

on

370

0.6

0.1

to investigate the effect of different kinetic

320

0.7

0.2

process inside the CSTR, in addition to

Storey and Donnalley
(2000) [11]

the

0.6

performance, some sample simulation

Storey et al.(1998)
[25]

representing

Temperature (K)
220
270

170

Roth et al. (1997) [34]

Storey and Choate

(1997) [13]

parameters

0.8

under both steady and transient states,

parameters

= +

Ivan and Kennedy

(1990) [24]

P-tCl is the tert-chloride chain

[P-tCl]0 is the total number of polymer chains

parameters

pressures and initializing systems were

Guhaniyogi et al.
(1982)[28]

= +
Where is the concentration of
instantaneously active growing chains

Conventional tertiary alkyl

chloride initiators

ASPEN Plus V 7.2, and the effect of

0.9

dimensions, operating temperatures and

Balogh et al. (1994)

[32]

Gyor et al. (1991) [29]

[ ]
=

TiCl4

The simulation was implemented in

various

Taylor andWilliams
(1969)[19]

, + ,
=

BCl3 and CH3Cl

ZnO

many

120

Table 1. Proposed IB Polymerization kinetics

TiCl4

include

SIMULATION RESULTS

models have been proposed for each of these steps

Stannic Chloride

equations

representation of the reactor behavior, the algorithm for the model is shown in Figure 2 (B).

various kinetic

Kinetic Investigation

Conversion

parameters were integrated using a FORTRAN code to allow for a more representative

involves an initiation, propagation, chain transfer

Initiator

Steam quality

Yield

all side reactions and oligomers produced, as well as hydrodynamics and mass/heat transfer

TiCl4, etc. (Figure 1). Generally, the liquid phase

and chain termination steps,

Results

thermodynamic models were programmed into Aspen Plus. The reaction kinetics, incorporating

coinitiators include AlCl3, (alkyl)AlCl2, BF3, SnCl4,

of

Heat produced

relevant components were entered into Aspen Properties, and the polymerization

and a Lewis acid coinitiator. Typical Lewis acid

polymerization

Phsyico-chemical
properties

YES

Concentration and
Temperature profiles

Operating
Conditions

Geometry

NO

hydrodynamics, heat and mass transfer and reaction kinetics. The physical properties of all

typically composed of two components: an initiator

electrophillic

Convergence?

Hydrodynamics and
mass transfer

momentum

mechanistically complex. The initiating system is

Empirical
correlation
s

schemes for energy and mass and mass

integration would also be investigated .
[7] L. Balogh, Z. Fodor, T. Kelen, R. Faust, Macromolecules 27 (1994) 4648-4651.
[8] M. Roth, M. Patz, H. Freter, H. Mayr, Macromolecules 30 (1997) 722-725.
[9] R.F. Storey, K.R. Choate, Macromolecules 30 (1997) 4799-4806.
[10] R.F. Storey, C.L. Curry, L.B. Brister, Macromolecules 31 (1998) 1058-1063.
[11] C. Paulo, J.E. Puskas, S. Angepat, Macromolecules 33 (2000) 4634-4638.
[12] M. Bahadur, T.D. Shaffer, J.R. Ashbaugh, Macromolecules 33 (2000) 9548-9552.
[13] R.F. Storey, A.B. Donnalley, Macromolecules 33 (2000) 53-59.

0
104

105

106

107

Ea (J/kmol)

108

109

Figure 3. Sample Simulation results (Top), Sensitivity

Analysis (Bottom)

[ [14] H. Schlaad, Y. Kwon, L. Sipos, R. Faust, B. Charleux, Macromolecules 33 (2000) 8225-8232.

[15] L. Sipos, P. De, R. Faust, Macromolecules 36 (2003) 8282-8290.
[16] P. De, R. Faust, Macromolecules 39 (2006) 7527-7533.
[17] M. Chmel, M. Marek, O. Wichterle, Journal of Polymer Science Part C: Polymer Symposia 16 (1967) 833-839.
Acknowledgement: The authors would like to thank Lubrizol for the financial support of this project.

Steady State Polyisobutylene Production (kg/s)

p-methylstyrene

Hydrodynamic models
/ Trubulence theory

ko-Initiation Effect on PIB conversion

and

Variables
Model equations
solved numerically

Ea Effect on PIB conversion

isoprene

Reactor
Model

Experiment

Hydrodynamic
and Transport
Parameters

Absorptionreaction theory

Polyisobutylene Conversion

like

Guess initial
values

Inputs

be used to describe and optimize the process have been very limited. Therefore The overall
objective of this project aims at the development of a rigorous kinetic based Aspen Plus

Pressure, Temperature,
Mixing speed, reactor size,
Kinetics, thermodynamic
data..