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Kinetic simulation of living carbocationic

polymerizations. II. Simulation of living
isobutylene polymerization using a
mechanistic model

ARTICLE in EUROPEAN POLYMER JOURNAL · JANUARY 2005

Impact Factor: 3.24 · DOI: 10.1016/j.eurpolymj.2004.08.006

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 EUROPEAN
POLYMER
European Polymer Journal 41 (2005) 1–14
JOURNAL
www.elsevier.com/locate/europolj

Kinetic simulation of living carbocationic polymerizations.

II. Simulation of living isobutylene polymerization
using a mechanistic model
Judit E. Puskas a,*, Sohel Shaikh b, Kevin Z. Yao c,
Kim B. McAuley c, Gabor Kaszas d
a
Macromolecular Engineering Research, Department of Polymer Science, The University of Akron, Akron,
OH 44325-3909, USA
b
Department of Chemical and Biochemical Engineering, The University of Western Ontario, London, ON, Canada N6A
c
Department of Chemical Engineering, Queen’s University, Kingston, ON, Canada K7L 3N6
d
Lanxess Inc., 1265 Vidal St. South, Sarnia, ON, Canada N7T 7M2

Received 14 July 2004; received in revised form 30 July 2004; accepted 2 August 2004
Available online 25 September 2004

Abstract

This paper discusses the kinetic simulation of TiCl4––coinitiated living carbocationic isobutylene (IB) polymeriza-
tions governed by dormant-active equilibria, using a mechanistic model. Two kinetic models were constructed from
the same underlying mechanism: one using a commercial simulation software package (Predici
), and the other using
the method of moments. Parameter estimation from experimental batch reactor data with Predici yielded a rate con-
stant of propagation kp = 4.64 · 108 ± 2.75 · 108 L/mol s, with no constraints imposed. This agrees with kp data meas-
ured with diffusion clock and competition methods, but disagrees with kinetically obtained kp values. Estimation of rate
constants with Predici
and the GREG parameter estimation software packages revealed that it was difficult to estimate
the complete set of kinetic parameters, due to correlated effects of the parameters on model predictions. Estimability
analysis confirmed that some of the strongly correlating parameters could not be estimated simultaneously using the
available experimental data. Using kp = 6 · 108 ± 2.75 · 108 L/mol s measured by Mayr, and using starting estimates
of other rate constants defined by experimentally observed correlations, yielded the set of rate constants required for
the simulations. Both kinetic models yielded good agreement with experimental data, with the exception of Mw values
that slightly diverged from the theoretically predicted
Mw
Mn = constant relationship. This may indicate the occur-
rence of a minor side reaction. However, the kp/k
1 = 17.5 L/mol average run length calculated from measured and sim-
ulated MWD data agrees well with earlier literature values.
 2004 Published by Elsevier Ltd.

Keywords: Living carbocationic polymerization; Isobutylene; Modeling; Kinetics; Mechanism; Run length

*
Corresponding author. Tel.: +1 330 972 6203; fax: +1 330 972 5290.
E-mail address: jpuskas@uakron.edu (J.E. Puskas).

0014-3057/$ - see front matter  2004 Published by Elsevier Ltd.

doi:10.1016/j.eurpolymj.2004.08.006
2 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14

Nomenclature

I initiator, 2-chloro-2,4,4-trimethyl-pentane k
0 rate constant of intermediate dissociation,

(TMPCl) s
1
IB isobutylene K0 k0/k
0, equilibrium constant of intermediate
LA Lewis acid (TiCl4––titanium tetrachloride) formation, L/mol
M monomer, isobutylene (IB) k1 ionization rate constant of form active spe-
PIB polyisobutylene cies with monomeric gegenion, s
1
MeCl methyl chloride k
1 deactivation rate constant of active species
MeCHx methylcyclohexane with monomeric gegenion, s
1
Hx hexane K1 k1/k
1, equilibrium constant of the forma-
DtBP di-tert-butylpyridine, proton trap tion of active species with monomeric
ED electron pair donor gegenion
[] concentrations of individual species, mol/L k2 ionization rate constant of form active spe-
[ ]0 initial concentrations of individual species, cies with dimeric gegenion, L/mol s
mol/L k
2 deactivation rate constant of active species
MW molecular weight with dimeric gegenion, s
1
Mn number average molecular weight K2 k2/k
2, equilibrium constant of the forma-
Mw weight average molecular weight tion of active species with dimeric gegenion,
DPn number average chain length L/mol
DPw weight average chain length u0 zeroth moment of dormant polymer chains
MWD M w =M n , molecular weight distribution uc0 zeroth moment of intermediate complex
I * LA initiator/Lewis acid intermediate ud0 zeroth moment of polymer chains with
I+LA
active initiator with monomeric gegenion dimeric counterions
Iþ LA
2 active initiator with dimeric gegenion um0 zeroth moment of polymer chains with
PIB-Cl dormant tertiary chloride capped polyiso- monomeric counterions
butylene chain ut0 total zeroth moment (u0 + uc0 + ud0 + um0)
Pn * LA polymer/Lewis acid intermediate with chain u1 first moment of dormant polymer chains
of n, n P 3 uc1 first moment of intermediate complex
Pn-Cl dormant, tert-chloride capped polymer ud1 first moment of polymer chains with dimeric
chain of length n, where n P 3 counterions


Pþ n LA active growing chain of length n, with mono- um1 first moment of polymer chains with mono-
meric Lewis acid gegenions n P 3 meric counterions


Pþ n LA2 active growing chain of length n, with dimer ut1 total first moment (u1 + uc1 + ud1 + um1)
Lewis acid gegenions n P 3 u2 second moment of dormant polymer chains
kp propagation rate constant of polymeriza- uc2 second moment of intermediate complex
tion, L/mol s ud2 second moment of polymer chains with
k 00p overall propagation rate constant of polym- dimeric counterions
erization, L3/mol3 s um2 second moment of polymer chains with
k0 rate constant of intermediate formation, L/ monomeric counterions
mol s ut2 total second moment (u2 + uc2 + ud2 + um2)

1. Introduction uniform polymers with living/controlled carbocationic

Living polymerization is characterized by the ab-
sence of significant chain transfer or irreversible chain
termination reactions. Living conditions were first
achieved in anionic polymerization [1]. Essentially liv-
ing conditions in carbocationic systems had been
achieved experimentally as early as 1974 [2]. Systematic
research in Kennedys group in the 1980s led to the suc-
cessful production of high molecular weight and nearly
polymerization [3]. By the mid-1990s, living/controlled
radical polymerization was also a reality [4]. Living
polymerization provides control over the molecular
weight (MW) and the architecture of the polymer
produced, and therefore is a preferred method of
macromolecular engineering [5–7]. In both living carbo-
cationic and radical polymerizations there is a reversi-
ble equilibrium between dormant and active chain
ends [7–10].
 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14 3

Pn Pn I + LA

In the living carbocationic polymerization of isobutylene

k-0 k0 Path B
(IB), it has been demonstrated that the active initiating Path A
and propagating centers are paired ions [9,11].
I*LA
PIB-Cl þ LA PIB == LA + LA
k-1 k-2 k2
where PIB-Cl is the dormant PIB chain capped with a k1
I+LA- I+LA2-
tertiary chloride group, and LA denotes the Lewis acid
coinitiator. The polymerization rate of IB is first-order
+M kp +M kp
in monomer, but under certain conditions apparent zero
order has also been reported [12,13]. The rate is first-
+M +M
order in initiator for a variety of initiating systems kp Pn+LA- Pn+LA2-
kp
[14–16]. This implies that the propagation is a simple k2
k1 k-1 + LA
bimolecular reaction between active chains and mono- k-2
mer. However, the polymerization rate has shown both
Pn*LA
first-order and second-order dependence on Lewis acid
(TiCl4) [15–26]. This close to second-order behavior
k0 k-0
was attributed to the fact that TiCl4 may form bimolec-
ular complex gegenions [25,26]. It was also suggested
that the propagation involves both monomeric and Pn + LA
dimeric counterions [27]. The rate of polymerization
Scheme 1. Comprehensive mechanism proposed for living IB
decreases with increasing temperature. This phenome-
polymerization.
non manifests itself as an ‘‘apparent negative activation
energy’’ [14,22,28,29]. These facts indicate that the
polymerization rate is a complicated function of all
the factors during a polymerization. When interpreting kp
the influences of these factors on the polymerization K1,eq=k1/k-1 +M
rate, the equilibrium between active and dormant chains
plays a key role. The shift of the equilibrium is governed k1 kp k-1
by many factors, including concentrations of initiator, I + LA I* Pn* Pn + LA
k-1 +M
k1
Lewis acid, monomer, additives, such as proton trap
and electron pair donors (EDs), as well as temperature Scheme 2. Simplified model of living IB polymerization.
and solvent polarity [14–26].
The comprehensive mechanistic model, shown in
Scheme 1, was conceived by Puskas group [15,25,26] 2. Kinetic background
for 2-chloro-2,4,4-trimethylpentane (TMPCl)/TiCl4 ini-
tiated living IB polymerization. In this model system, 2.1. The proposed scheme
the structure of the TMPCl initiator mimics that of the
growing polymer chains. It has been demonstrated that The proposed comprehensive mechanism [15] in-
if ki  kp is assumed for this system, it greatly simplifies volves a series of consecutive and competitive reactions.
the kinetic derivations [17]. Subsequently this assump- Firstly, the initiator and Lewis acid form an intermedi-
tion was verified experimentally; kp = 6 ± 4 · 108 L/mol s ate, I * LA, through an equilibrium involving rate con-
was measured by the diffusion clock method [30] and stants k0 and k
0. This intermediate species can
with kp/k
1 = 16.5, kp  3ki [17,23]. In previous papers, undergo two reactions as shown by the Paths A and
a Predici simulation of a simplified version of the ki- B. In Path A, this intermediate species becomes a mono-
netic model, as shown in Scheme 2, was described meric active initiator through an equilibrium involving
[25,26]. The rate constants that were used in the simple rate constants k1 and k
1. The monomeric active initia-
model were combinations of the true kinetic constants tor can polymerize monomers, leading to growth of the
in the proposed comprehensive model. The current pa- active chain. An active growing chain of any length, n,
per is particularly aimed at deconvoluting appropriate can transform back to a polymer/Lewis acid intermedi-
values for the true constants, regardless of the different ate through an equilibrium involving k
1 and k1. In Path
experimental conditions (e.g., different initiator and B, the initiator/Lewis acid intermediate can incorporate
Lewis acid concentrations), and using them in the com- an additional Lewis acid to form a dimeric active initia-
prehensive mechanistic model to simulate living IB tor through an equilibrium involving rate constants k2
polymerization. and k
2. The dimeric active initiator can then propagate
4 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14
by adding monomer. It has been shown that the dimeric
gegenion must form by a two-step process [11,24,31].
Halogenated titanium compounds are known to form
neutral dimers in a variety of crystal structures and
also under cryogenic conditions, but with a very lim-
ited stability range [32,33]. The existence of neutral
dimeric Ti2Cl8 under dilute polymerization conditions
([TiCl4]0  10
2–10
1 mol/L) has never been demon-
strated experimentally. In Scheme 1, the dimer forma-
tion follows a two-step course as suggested earlier
[11,24,31]. In the first step, the initiator/Lewis acid or
polymer/Lewis acid intermediate dissociate forming
monomeric counteranions, which in turn can react with
additional Lewis acid to form dimeric counteranions.
The species with dimeric counteranion can propagate
with monomer, or can also release Lewis acid and trans-
form back to an initiator/Lewis acid or polymer/Lewis
acid intermediate by an equilibrium reaction involving
k
2 and k2. The polymer/Lewis acid intermediate,
Pn * LA, formed from both Paths A and B can undergo
equilibrium reactions to produce dormant chains, Pn,
and free Lewis acid.
The mechanism in Scheme 1 accounts for a number
of important experimental observations: the depend-
ence of polymerization rate on Lewis acid can be either
first or second order, or in between, depending on the
actual Lewis acid concentration and other experimental
conditions [17–26]; the true propagation rate constant
kp, can be as high as 109 L/mol s as determined by dif-
fusion clock methods [30,34–36] while the kinetically-
determined rate constant (a combination of K0K1kp
and K0K2kp in Scheme 1) can be as low as 104 L/mol s.
Table 1 lists the high and low values of kp obtained by
various research groups using different experimental
techniques. The inconsistency in reported kp values
has been discussed by Plesch [41,43] and still remains
unresolved [44]. While the mechanistic model shown
in Scheme 1 provides a plausible solution to this appar-
ent discrepancy, as yet there has been no direct experi-
mental confirmation of the existence and the chemical
Table 1
kp values in carbocationic IB polymerizations obtained by various methods
kp (L/mol s) Initiating system
3
6 · 10 AlBr3/TiCl4
7.9 · 105 Light/VCl4
1.2 · 104 Et2AlCl/Cl2
9.1 · 103 Ionizing radiation
1.5 · 108 Ionizing radiation
6 · 108 R-Cl/TiCl4
7 · 108 IB n-mer/TiCl4
4.7 · 108 TMP-Cl/TiCl4
1.7 · 109 TMP-Cl/BCl3
a
Diffusion clock/competition experiments.
nature of the proposed intermediates, I * LA and
Pn * LA. Several investigators have suggested the exist-
ence of various intermediates and suggested pathways
for their formation. For example, the formation of
polarized (stretched or activated, more-covalent-than-
ionic) dipole intermediates in the reaction of TMPCl
or PIB-Cl with TiCl4 (Winstein spectrum) was sug-
gested by various researchers [17,45]. Plesch suggested
the formation of a monomer-solvated carbocation
intermediate [43] and in this case high monomer con-
centration would result in first-order propagation with
the intermediate. Sigwalt argued that this suggestion
was not convincing since low kp values were also ob-
served at low monomer concentrations [46,47], and in
turn he suggested a two-step propagation with the
formation of solvated carbocationic intermediates
[48]. With this, the apparent second-order rate con-
stant obtained in kinetic experiments would be
kp,app = KSM * kp where KSM is the constant for the
equilibrium between solvated carbocation and mono-
mer-complexed solvated carbocation, this latter pro-
pagating by unimolecular rearrangement. Scheme 1
proposes the formation of polymerization-active carbo-
cations via intermediates involving the initiator and/or
the dormant polymer chain and the Lewis acid. It
may be reasonable to assume that these intermediates
are polarized species. Following the formation of



Pþ þ
n == LA or Pn == LA2 propagation could proceed
via a collision of these species with monomer as shown
in Scheme 1, or via a two-step reaction as suggested by
Sigwalt: first by monomer solvation, followed by prop-
agation via rearrangement. In this latter case the kp in
Scheme 1 would also represent a composite rate con-
stant involving the monomer solvation equilibrium
constant and the true rate constant of propagation
(KSM * kp). Scheme 1 and Sigwalts model show similar-
ities in terms of reasoning that the discrepancy between
kinetically obtained rate constants and those measured
by the diffusion clock method could be due to various
pre-equilibria.
Solvent T/C Reference
Heptane
14 [37]
In bulk
20 [38]
CH3Cl
48 [39]
CH2Cl2
78 [40,41]
In bulk
78 [42]
CH2Cl2
78 [30]a
Hexanes/CH3Cl
80 [34]a
Hexanes/CH3Cl
80 to
40 [35]a
Hexanes/CH3Cl
80 to
40 [36]a
 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14 5

As mentioned earlier, this paper discusses the decon- Table 2

volution of kinetically obtained rate constants using the Reactions
mechanistic model of Scheme 1. I + LA M I * LA k0, k
0
I * LA M I+LA
k1, k
1
2.2. Kinetic modeling I  LA þ LA $ Iþ LA
2 k2, k
2
Iþ LA
þ M ! Pþ n LA


ki  kp
Based on Scheme 1, a kinetic model was developed I LA2 þ M ! Pn LA

þ
þ
2 ki  kp



using Predici
, an open-ended integrated polymerization Pþ þ
n LA þ M ! Pnþ1 LA kp
Pn LA2 þ M ! Pnþ1 LA

þ
þ
kp
software that is based on the discrete Galerkin h-p

2
Pþn LA ! Pn  LA k
1
Method [49]. It allows unrestricted input of reaction rate þ
Pn  LA ! Pn LA

k1
constants, different types of polymer species, monomers Pþ

n LA2 ! Pn  LA þ LA k
2
and reactants, reaction steps and polymerization condi- Pn  LA þ LA ! Pþ

n LA2 k2
tions such as temperature and pressure [50]. During a Pn * LA ! Pn + LA k
0
typical dynamic simulation, the formation or consump- Pn + LA ! Pn * LA k0
tion of any of the individual species can be followed
either with respect to time or conversion. It also has
parameter estimation capabilities; based on a given material balance equations for each individual species.
kinetic model and sufficient experimental data, rate con- Because we have used TMPCl, essentially a dimer PIB,
stants can be estimated. Within the Predici environment, as the initiator in the experiments, we refer to the first
the series of reactions shown in Table 2, was written. polymeric species formed by propagation as P3 (Table
Independently, a set of ordinary differential equa- 3: Eqs. (g), (i) and (m)).
tions (ODEs) were derived as shown in Table 3 [51]. The method of moments was used to determine the
The model equations are composed of a set of dynamic weight and number average molecular weights of the

Table 3
Material balance equations for the comprehensive model
Low molecular weight species:
d½I
¼
k 0 ½I½LA þ k
0 ½I  LA (a)
dt
d½I  LA
¼ k 0 ½I½LA
k 2 ½LA½I  LA
ðk
0 þ k 1 Þ½I  LA þ k
1 ½Iþ LA
 þ k
2 ½Iþ LA

2 (b)
dt
þ

d½I LA 
¼ k 1 ½I  LA
ðk
1 þ k p ½MÞ½Iþ LA
 (c)
dt
d½Iþ LA
2
¼ k 2 ½I  LA½LA
ðk
2 þ k p ½MÞ½Iþ LA
2 (d)
dt
d½M X 1 X1
¼
k p ½Mð½Iþ LA
 þ ½Pþ LA
 þ ½Iþ LA

i¼3 i 2þ ½Pþ LA

i¼3 i 2 Þ (e)
dt
d½LA X 1 X 1
¼ k
0 ð½I  LA þ ½P  LAÞ
k 0 ½LAð½I þ
i¼3 i
P Þ
k 2 ½LAð½I  LA
i¼3 i
dt P1
P1 þ
(f)
þ i¼3 ½Pi  LAÞ þ k
2 ð½I þ LA2  þ i¼3 ½Pi LA2 Þ

High molecular weight species:

d½Pþ3 LA 
¼ k p ½Mð½Iþ LA

½Pþ
þ

3 LA Þ
k
1 ½P3 LA  þ k 1 ½P3  LA (g)
dt
þ

d½Pi LA 



¼ k p ð½Pþ þ þ
i
1 LA 
½Pi LA Þ
k
1 ½Pi LA  þ k 1 ½Pi  LA i ¼ 4    1 (h)
dt
þ

d½P3 LA2 
¼ k p ½Mð½Iþ LA
þ
þ

2 
½P3 LA2 Þ
k
2 ½P3 LA2  þ k 2 ½P3  LA½LA (i)
dt
þ

d½Pi LA2 



¼ k p ½Mð½Pþ þ þ
i
1 LA2 
½Pi LA2 Þ
k
2 ½Pi LA2  þ k 2 ½P3  LA½LA i ¼ 4    1 (j)
dt
d½P3  LA


¼ k
1 ½Pþ þ
3 LA 
ðk
0 þ k 1 þ k 2 ½LAÞ½P3  LA þ k
2 ½P3 LA2  þ k 0 ½P3 ½LA (k)
dt
d½Pi  LA


¼ k
1 ½Pþ þ
i LA 
ðk
0 þ k 1 þ k 2 ½LAÞ½Pi  LA þ k
2 ½Pi LA2  þ k 0 ½Pi ½LA i ¼ 4    1 (l)
dt
d½P3 
¼ k
0 ½P3  LA
k 0 ½P3 ½LA (m)
dt
d½Pi 
¼ k
0 ½Pi  LA
k 0 ½Pi ½LA i ¼ 4    1 (n)
dt
6 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14

Table 4
Zeroth, first and second moments of polymer species
Intermediate complexes Polymer chains with monomeric counterions
P P
Zeroth moment uc0 ¼ ½I  LA þ 1 i¼3 ½Pi  LA um0 ¼ ½Iþ LA
 þ 1 þ
i¼3 ½Pi LA 


P P1
First moment uc1 ¼ 2½I  LA þ 1 i¼3 i½Pi  LA um1 ¼ 2½I LA  þ i¼3 i½Pi LA

þ
þ
P 2 P 2 þ

Second moment uc2 ¼ 22 ½I  LA þ 1 i¼3 i ½Pi  LA um2 ¼ 22 ½Iþ LA
 þ 1 i¼3 i ½Pi LA 

Polymer chains with dimeric counterions Dormant polymer chains

P1 þ
P
Zeroth moment ud 0 ¼ ½Iþ LA
2þ i¼3 ½Pi LA2  u0 ¼ ½I þ 1 i¼3 ½Pi 
P1 P1
First moment ud 1 ¼ 2½I LA2  þ i¼3 i½Pþ LA

þ

2 u1 ¼ 2½I þ i¼3 i½Pi 
P1 2 þ
P 2
Second moment ud 2 ¼ 22 ½Iþ LA
2þ i¼3 i ½Pi LA2  u2 ¼ 22 ½I þ 1 i¼3 i ½Pi 

Table 5 types of polymeric species. Instead, the total of all of the

Moment balance equations second moments can be determined from zeroth and first
dum0 moments:
¼
k
1 um0 þ k 1 uc0 (a)
dt
dud 0 dut2
¼ k 2 ½LAuc0
k
2 ud 0 (b) ¼ k p ½Mð2um1 þ um0 þ 2ud 1 þ ud 0 Þ ð3Þ
dt dt
duc0
¼ k
1 um0
ðk 1 þ k
0 þ k 2 ½LAÞuc0
dt (c) The number average and weight average degree of
þk
2 ud 0 þ k 0 ½LAu0
polymerization can be expressed by three leading mo-
du0
¼ k
0 uc0
k 0 ½LAu0 (d) ments. As the polymer chains are a combination of four
dt
dum1 types of polymer species, sums of the individual mo-
¼ k p Mum0
k
1 um1 þ k 1 uc1 (e) ments are required for the calculation of degree of
dt
dud 1 polymerization:
¼ k p ½Mud 0
k
2 ud 1 þ k 2 ½LAuc1 (f)
dt
duc1 ut1 um1 þ ud 1 þ uc1 þ u1
¼ k
1 um1
ðk 1 þ k
0 þ k 2 ½LAÞuc1 (g) DPn ¼ ¼
dt ut0 um0 þ ud 0 þ uc0 þ u0
þk
2 ud 1 þ k 0 ½LAu1
du1 2½I0 þ ½M0
½M
¼
k 0 ½LAu1 þ k
0 uc1 (h) ¼ ð4Þ
dt ½I0
d½M
¼
k p ½Mðum0 þ ud 0 Þ (i) ut2 ut2
dt
d½LA DPw ¼ ¼ ð5Þ
¼ k
0 uc0
k 0 ½LAu0
k 2 ½LAuc0 þ k
2 ud 0 (j) ut1 um1 þ ud 1 þ uc1 þ u1
dt
The material balance equations, moment equations, and
equations for degree of polymerization required to sim-
polymeric species. These moments are defined in Table 4 ulate the polymerization process are in Table 3 (Eqs.
and the corresponding moment differential equations are (a)–(d)) Table 5 (Eqs. (a)–(i)) and Eqs. (1)–(5). The dy-
given in Table 5 [51]. namic model equations were solved using DDASAC
From the moment definitions, the total of these zer- [52].
oth moments (ut0 = u0 + uc0 + um0 + ud0) is the total
concentration of polymer chains and other initiator- 2.3. Determination of initial estimates of rate constants
derived species present, which equals the initial concen-
tration of initiator. The total of the first moments 2.3.1. Experimental kinetic measurements
(ut1 = u1 + uc1 + um1 + ud1) is the total number of moles Based on Scheme 1, selected rate constants can be de-
of monomer units in the polymer chains and initiating rived experimentally from initiator and monomer con-
species, which equals the moles of monomer units ini- sumption data, to be used as initial estimates for the
tially in the initiator, plus the monomer consumed: parameter estimation. Assuming that experimental
conditions have been selected that the polymerization
ut0 ¼ ½I0 ð1Þ
proceeds either predominantly by Path A or predomi-
nantly by Path B, simplified expressions were derived
ut1 ¼ 2½I0 þ ½M0
½M ð2Þ
from Scheme 1 to describe the time-varying behavior
Notice that balances on the second moments of chain of the initiator [I] and monomer [M] concentrations:
length distribution are not included in Table 3 as it is the detailed derivations are given in Appendix A (Path
unnecessary to calculate second moments for the various A) and Appendix B (Path B).
 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14
Path A
½I0
ln ¼ K 0 k 1 ½LA0 t
½I
½M0
ln ¼ k p K 0 K 1 ½I0 ½LA0 t
½M
Employing Eqs. (6) and (7), K0k1 = 0.22 L/mol s and
K0K1kp = 3.4 L2/mol2 s were calculated from previously
published experimental initiator and monomer con-
sumption data in Path A [15].
Path B
½M0
ln ¼ K 0 K 2 k p ½I0 ½LA20 t
½M C2 :
In Path B, that is, under conditions normally used in liv-
ing IB polymerizations, initiation is nearly instantaneous
and initiator consumption cannot be followed experi-
mentally. After a very fast initiation period, [Pn] = [I]0.
In classical living polymerization this simplification is
routinely used in formulating rate equations for mono-
mer consumption. Also, in case of instantaneous ini-
tiation the monomer consumed during initiation is
neglected. In contrast, in Path A, initiation and propa-
gation was found to proceed simultaneously, so these
simplifications cannot be considered. In Path B, experi-
mental data have revealed a fractional order of 1.76 in
TiCl4 [15], which is in good agreement with the range
of 1.7–2.2 reported by other researchers [11,16,19,24].
½M0
ln ¼ k 00p ½I0 ½LA1:76
½M
Here k 00p is the experimentally measured apparent rate
constant. This indicates that in reality, both Paths A
and B proceed simultaneously, with Path B dominating.
Using Eq. (9), constant k 00p ¼ 52 L3/mol3 s was obtained
from experimental monomer consumption data [15].
With the interpretation in Eq. (8), K0K2kp = 52 L3/
mol3 s. Eqs. (6)–(8) were derived with several assump-
tions and should be viewed as simplified rate expres-
sions, but they provide means to establish initial
estimates for the simulations.
Selected rate constants in IB polymerizations have
been measured or derived independently. For instance,
‘‘diffusion clock’’ and competition experiments methods
yielded kp  108 L/mol s [30,35,36]. As discussed earlier,
this high value is contradicting earlier data, presented
in Table 1, with the exception of kp obtained from irra-
diation-initiated IB polymerization. Industrial experi-
ence supports the close to diffusion-limited high value
[53], therefore we accepted this value. Later it will be
shown that parameter estimation also supports a high
kp value. Published capping rate constants, although de-
rived from differing interpretations, were in the range of
3–5 · 107 s
1 (Puskas and Peng [26]: k
1 = 3.9 · 107 s
1
7
(TMPCl); Kim and Faust [55]: k
1 = 5.0 · 107 s
1
(TMPCl) and k
1 = 3.4 · 107 s
1 (PIB-36mer). Using
ð6Þ kp = 6 · 108 L/mol s we get K0K1 = 5.7 · 10
9 L/mol and
K0K2 = 8.7 · 10
8 L2/mol2, which confirms that both
equilibria are dramatically shifted toward the dormant
ð7Þ polymer chains Pn-Cl. From K0k1 = 0.22 L/mol s and
K0K1 = 5.7 · 10
9 L/mol we get k
1 = 3.9 · 107 s
1. This
agrees very well with published capping rate coefficients,
thus we assumed this value for k
2 and determined
K0k2 = (k0/k
0) Æ k2 = 3.38 L2/mol2 s.
As a result, the following correlations have been
established:
C1 : k 1 K 0 ¼ k 1  ðk 0 =k
0 Þ ¼ 0:22 L=mol s ð10Þ
ð8Þ
k 2 K 0 ¼ k 2  ðk 0 =k
0 Þ ¼ 3:38 L2 =mol2 s ð11Þ
The correlation between the parameters will influence
the estimability of individual parameters.
2.4. PREDICI parameter estimation
For the PREDICI parameter estimation, the reaction
scheme in Table 2 was used. Table 6 lists initial rate con-
stant values and sets of estimated parameters. The initial
values for k0, k
0, k1 and k2 were established from the
correlations given in (10) and (11) by trial and error, fit-
ting experimental data [54]. The parameter estimation
routine in PREDICI is based on the damped Gauss–
Newton method [56,57] and has the ability to converge
well even with bad starting values. Seven experimental
data sets were used in the simulation [15]. First, all
ð9Þ parameters were estimated simultaneously. The simula-
tion did converge with kp = 6 * 108 L/mol s as a starting
estimate without any constraints imposed, although with
high error within the 90% confidence intervals; the data
are listed as Set 1 in Table 6. It is interesting to note that
kp converged to a value of 4.64 * 108 ± 2.75 * 108 L/mol s.
In contrast, the simulation was unable to converge with
kp = 104 L/mol s as a starting estimate. This further sup-
ports the high kp values obtained in diffusion clock and
competition experiments [30,35,36]. The values for k
1
and k
2 converged to 1.77 and 2.75 * 107 s
1, close to
the initial values. However, k0, k
0, k1 and k2 carried very
large errors and did not satisfy the correlations estab-
lished in (10) and (11). Next we fixed kp = 6 * 108 L/mol s
and k
1 = k
2 = 3.9 * 107 s
1, and estimated k0, k1 and
k2. Set 2 shows that the error is still high. In the next step
we enforced the correlations defined in Eqs. (10) and (11)
using interpreter functions in Predici [57]. Set 3 shows
that k0 and k
0 still carry very high error. As was deter-
mined from the estimability analysis, these parameters
were correlated and hence could not be estimated simul-
taneously. Therefore in Set 4, we fixed the value of k
0 to
3.9 * 107 s
1. Set 4 shows the estimated k0 with low error
within the 90% confidence interval. The parameters in
Set 4 were used for the simulations with Predici. It should
8 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14

Table 6
Initial parameter values and parameter estimates used in simulations
Parameter Initial values Set 1 ± CIa (estimating all) Set 2 ± CI (estimating k0, k1, k2)
1(a): Estimates without constraints
k0 (L/mol s) 1.56 * 108 2.75 * 108 ± 2.79 * 108 7.96 * 107 ± 3.97 * 107

1
k
0 (s ) 3.90 * 107 1.13 * 108 ± 7.62 * 108 3.90 * 107
k1 (s
1) 5.50 * 10
2 1.20 * 10
2 ± 1.23 * 10
2 1.72 * 10
2 ± 1.23 * 10
2
k
1 (s
1) 3.90 * 107 1.71 * 107 ± 1.77 * 107 3.90 * 107
k2 (L/mol s) 8.45 * 10
1 5.88 ± 3.93 3.50 ± 1.47
k
2 (s
1) 3.90 * 107 5.90 * 107 ± 2.75 * 107 3.90 * 107
kp (L/mol s) 6.00 * 108 4.64 * 108 ± 2.75 * 108 6.00 * 108

Set 3 ± CI (estimating k0, k
0) Set 4 ± CI (estimating k0)

1(b): Estimates with constraints
k0 (L/mol s) 1.72 * 108 ± 3.84 * 108 1.51 * 108 ± 2.03 * 107

1
k
0 (s ) 4.48 * 107 ± 1.16 * 108 3.90 * 107
k1b (s
1) 5.73 * 10
2 5.68 * 10
2
k
1 (s
1) 3.90 * 107 3.90 * 107
k2b (L/mol s) 8.80 * 10
1 8.73 * 10
1
k
2 (s
1) 3.90 * 107 3.90 * 107
kp (L/mol s) 6.00 * 108 6.00 * 108
a
CI = 90% confidence interval.
b
The values of k1 and k2 are dictated by correlations defined in Eqs. (10) and (11).

be noted here that the parameters estimated for k0, k
0,

k1 and k2 in all four sets gave reasonable agreement with 0.05 Predici
ODE
experimental data. However, the model is very sensitive
to kp/k
1. Since kp and k
1 are highly correlated we 0.04
had good agreement between simulation and experimen-
[TMPCl], mol/L

tal data with either low or high kp data as long as kp/k
1 0.03
was kept constant at 16.5 L/mol. We do not intend to
argue that agreement between experimental and simu-
0.02
lated data alone can prove any proposed mechanisms.
Kinetic simulation can only disprove a proposed mecha-
nism if it shows serious discrepancy between experimen- 0.01
tal and simulated plots. In our particular case, if we
accept independently measured capping constants in 0.00
the range of 107 s
1, good agreement can only be found 0 200 400 600 800
for high propagation rate constant (kp  108 L/mol s). time (s)

Fig. 1. Comparison of experimental and simulated initiator

2.5. Parameter estimability analysis using the ODE model
Attempts were also made to estimate the kinetic
parameters using the same batch reactor data [15] the
ODE version of the model in Tables 3–5 and the GREG
parameter estimation software [52]. Before using GREG
to estimate the parameters, it was confirmed that the Pre-
dici model and the ODE model yielded practically iden-
tical simulation results when using the same parameters;
representative examples for a Path A simulations are
shown in Figs. 1–3. In all other figures, only the PRE-
DICI results are shown. Pooled variances for measured
molecular weight and initiator and monomer concentra-
tions were determined from replicate experiments at two
different experimental settings (four replicate Path B runs
with [TMPCl]0 =0.004 mol/L and [TiCl4]0 = 0.032 mol/L,
consumption plots for Path A: [IB]0 = 2.0 mol/L, [TMPCl]0 =
0.05 mol/L, [DtBP]0 = 0.007 mol/L. Hx/MeCl=60/40 v/v; Exper-
imental: [TiCl4] = 0.05 mol/L (m), [TiCl4] = 0.025 mol/L (s);
Temperature:
80 C; Simulation parameters: Set 4 (Table 1).
and two Path A runs with [TMPCl]0 = 0.05 mol/L and
[TiCl4]0 = 0.0125 mol/L), and were supplied to the
GREG parameter estimation software [58].
Attempts to estimate all of the model parameters
simultaneously failed, even after the model was re-
parameterized in an attempt to improve the numerical
conditioning of the parameter estimation problem (i.e.,
expressing the model in terms of natural logarithms to
ensure that all parameters estimated would have the
same order-of-magnitude size). Simulations revealed
 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14 9

To further investigate the correlated effects of the

2.0
Predici parameters on the model predictions and to determine
ODE
which subsets of the model parameters can be esti-
mated together, a detailed parameter estimability anal-
1.5 ysis [59] was performed, after including the correlations
in Eqs. (10) and (11) in the model. It was found that,
[M], mol/L

among the four parameters, k
0, k0, k1 and k2, it is

1.0 impossible to estimate any two parameters simultane-
ously. k
0 and k0 are correlated through the kinetic
mechanism (K0 = k0/k
0), and k1 and k2 are related
0.5
by the correlations defined in (10) and (11). Hence,
only one of these parameters can be included in the
set of parameters to estimate using the current set of
0.0
0 200 400 600 800 experimental data. If additional measurements were
time (s) available, e.g., measurements of the concentration of
the I * LA or Pn * LA intermediates, then more kinetic
Fig. 2. Comparison of experimental and simulated monomer parameters could be estimated. Without any additional
consumption plots for Path A: [TMPCl]0 = 0.05 mol/L, [IB]0 = measurements to compare with model predictions,
2 mol/L, [DtBP]0 = 0.007 mol/L. Hx/MeCl=60/40 v/v; Experi- however, multiple sets of values for these four param-
mental: [TiCl4] = 0.05 mol/L (m), [TiCl4] = 0.025 mol/L (s);
eters will give the same model predictions as the
Temperature:
80 C; Simulation parameters: Set 4 (Table 1).
parameter estimates in Set 4, which were used to sim-
ulate the experimental results.

100 2.6. Simulation of living IB polymerization using the

proposed model of Scheme 1
Predici
80 ODE
Figs. 1 and 2 show experimental [15] and simulated
initiator and monomer consumption plots for Path A.
60 The agreement is very good. As discussed above, initia-
DPn, DPw

tor and monomer consumption is simultaneous under

40
20
0 ble. The MWD is slightly lower than 2 during the entire
0.0 0.2 0.4 0.6
Conversion
Fig. 3. Experimental and simulated molecular weight vs
conversion plots for Path A: Experimental: Mn (s), Mw (m),
[TMPCl]0 = 0.05 mol/L, [TiCl4]0 = 0.025 mol/L, [IB]0 = 2 mol/L,
[DtBP]0 = 0.007 mol/L. Hx/MeCl=60/40 v/v; Temperature:

80 C; Simulation parameters: Set 4 (Table 1).
that nearly identical simulation results could be obtained
if certain parameters were adjusted in pairs. For exam-
ple, simulation results indicate that if the forward rate
constant k0 and the reverse rate constant k
0 are both
doubled, there are no significant changes in the model
predictions. The equilibrium position of the reaction is
maintained, and since both reactions are already very
fast, increasing their rates, together, has no discernable
effect on the molecular weights or reactant concentra-
tions. Similar conclusion applies to kp/k
1.
the experimental conditions used. As a consequence,
the degree of polymerization increases only slightly with
conversion, as shown in Fig. 3. The Mn prediction is
quite good, while Mw is slightly overestimated. This
could be attributed to the very low molecular
weights––loss of fractions during precipitation is inevita-
0.8
reaction.
In Path B, the simulated monomer consumption
shows very good agreement with experimental data as
can be seen from Fig. 4. The predicted Mn also shows
a good fit to experimental data (Figs. 5 and 6). However,
the Mw value becomes progressively underpredicted
with increasing conversion. This points to the existence
of possible side reactions. Therefore linear semilogarith-
mic monomer consumption plots together with linear
Mn––conversion plots, which are currently considered
as proof for living conditions, are insufficient to demon-
strate living conditions. The additional criterion of
Mw
Mn = constant [5] should also be considered when
evaluating living polymerizations. This is evident from
the simulated plots obtained with an ideal model, but
the experimental data deviates from this prediction.
Introduction of various possible side reaction scenar-
ios such as slow initiation, termination, transfer and
slow protic initiation into our model was unsuccessful.
10 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14

2.0 600

Predici Predici
500
1.5

400
[M], mol/L

DPn, DPw
1.0 300

200
0.5

100

0.0 0
0 2000 4000 6000 8000 0.0 0.2 0.4 0.6 0.8
time (s) Conversion

Fig. 4. Comparison of experimental and simulated monomer
consumption plots for Path B: [TMPCl]0 = 0.004 mol/L, [IB]0 =
2 mol/L, [DtBP]0 = 0.007 mol/L. Hx/MeCl=60/40 v/v; Experi-
mental: [TiCl4] = 0.064 mol/L (m), [TiCl4] = 0.04 mol/L (s);
Temperature:
80 C; Simulation parameters: Set 4 (Table 1).
Fig. 6. Experimental and simulated molecular weight vs
conversion plots for Path B: Experimental: Mn (s), Mw (m),
[TMPCl]0 = 0.004 mol/L, [TiCl4]0 = 0.064 mol/L, [IB]0 = 2 mol/
L, [DtBP]0 = 0.007 mol/L. Hx/MeCl=60/40 v/v; Temperature:

80 C; Simulation parameters: Set 4 (Table 1).

Mn and Mw values. More detailed studies are necessary

600
to find the cause of the Mw divergence.
Predici
500 2.7. Calculating the average run length l0 from Path A

400 Puskas et al. [9] introduced a method to calculate the

average run length l0 , defined as the average number of
DPn, DPw

300
monomer units incorporating in one active ionization
period, from MWD data using Eq. (12)
200 DPw l0
¼1þ ð12Þ
DPn ðDPn Þ
100
where l0 ¼ ðk p =k
1 Þ½M0 . Eq. (13) shows the form for
intermediate conversion.
0
0.0 0.2 0.4 0.6 0.8  
Conversion l ¼ 1 þ l0
1 1 þ ½M ð13Þ
2 ½M0
Fig. 5. Experimental and simulated molecular weight vs
conversion plots for Path B: Experimental: Mn (s), Mw (m), Subsequently Müller et al. [60] introduced another
[TMPCl]0 = 0.004 mol/L, [TiCl4]0 = 0.04 mol/L, [IB]0 = 2 mol/L, method:
[DtBP]0 = 0.007 mol/L, Hx/MeCl=60/40 v/v; Temperature:  

80 C; Simulation parameters: Set 4 (Table 1).
DPw 1 2
¼1þ
1 ð14Þ
DPn b X
where X = conversion and b = k
1/kp[I]0.
When TMP-Cl and PIB 36-mer were used as initiators, it Storey recently showed that average run length num-
was found that kp  3 * ki [23], but simulations con- bers could also be obtained from ‘‘rapid monomer con-
ducted using a ki value of 1–2 * 108 L/mol s did not show sumption’’ (RCM) data [28]. We now will show that l0
any noticeable difference when compared to simulations can also be obtained from Path A in IB polymerization.
with kp = ki. When slow irreversible termination was At the end of the reaction in Path A, when the initiator
introduced, a better fit was obtained for Mw in certain is consumed, polydispersity of 1.84 was obtained exper-
experiments [54], but in others led to discrepancies in imentally and simulation yielded a polydispersity of 1.88
the monomer consumption and Mn data. Introducing (Fig. 3). The conditions in Path A experiments, when
chain transfer caused a simultaneous reduction in both initiator and monomer consumption is simultaneous,
 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14 11

can be considered as the first ‘‘run’’ of a living polymer- that can polymerize, Eqs. (A.1) and (A.2) may be added
ization; initiation is complete only at the end of the reac- together to get:
tion. Using DPw/DPn = 1.88 and the DPn value of 40 at
full initiator conversion, l0 ¼ 35 was obtained from Eq. d½I d½I  LA dð½I þ ½I  LAÞ
þ ¼
(13). Using l0 ¼ ðk p =k
1 Þ½M0 [8], kp/k
1 = 17.5 L/mol is dt dt dt
calculated. This is in excellent agreement with that pub- ¼
k 1 ½I  LA þ k
1 ½Iþ LA
 ðA:3Þ
lished by Kaszas and Puskas [17] (kp/k
1 = 16.5 L/mol)
[I] + [I * LA] = [I]u, where [I]u is the concentration of
and Schlaad et al. [23] (kp/k
1 = 16.4 L/mol). Thus l0
unreacted initiator, thus Eq. (A.4) defines the rate of
can be obtained experimentally under Path A condi-
initiator consumption and polymer formation:
tions, where initiation will compete with propagation.
Under these conditions Mn and Mw will remain approx- d½Iu d½Pn 

¼ ðA:4Þ
imately constant, with the polydispersity for the most dt dt
probable distribution of MWD = 2. The MWD will start If the reactions involving k0 and k
0 are very fast,
to narrow only after initiation is complete. then we will have an initial rapid equilibration, after
which:
3. Conclusions k0
½I  LA ¼ ½I½LA ðA:5Þ
k
0
In conclusion, we can state that the reaction mecha-
nism proposed in Scheme 1 reconciles seemingly contra- so that Eq. (A.3) becomes:
dictory experimental findings (e.g., shifting TiCl4 order d½Iu
and discrepancy in rate constant values obtained with ¼
k 1 K 0 ½I½LA þ k
1 ½Iþ LA
 ðA:6Þ
dt
diffusion clock methods and kinetic measurements)
Now, if [I+LA
] is small due to the fast propagation
and can be used to simulate experimental results with
reaction of the ionized species, and [LA]  [LA]0, we
rate constants that satisfy the correlations imposed by
have:
the mechanism and/or independently measured rate con-
stants. This by no means can be considered as proof of d½Iu
¼
k 1 K 0 ½I½LA0 ðA:7Þ
the proposed mechanism. The existence and chemical dt
nature of the proposed intermediates must be proven Expanding (A.7) with 1/[I]u on both sides and substitut-
independently. However, in the absence of another ing (A.5) gives:
model that satisfies all the contradictory requirements
this model does not seem to be unreasonable. In addi- 1 d½Iu
k 1 K 0 ½I½LA0
k 1 K 0 ½LA0
 ¼ ¼ ðA:8Þ
tion, large-scale production data (confidential) demon- ð½Iu Þ dt ð½I þ ½I  LAÞ ð1 þ K 0 ½LA0 Þ
strates that the rate constant of propagation must be Assuming K0[I]0  1 (A.8) can be simplified to give
very high. (A.9):
1 d½Iu
Acknowledgment  ¼
k 1 K 0 ½I½LA0 ðA:9Þ
ð½Iu Þ dt

Financial support of Bayer Inc., Canada and Integrating (A.9) between the limits of [I]u,0 = [I]0 and
NSERC Canada is gratefully acknowledged. [I]u,t = [I]t + [I * LA]t
Z ½Iu;t Z t
d½Iu
¼
k 1 K 0 ½LA0 dt ðA:10Þ
½Iu;0 ½Iu t¼0
Appendix A. Path A
we get the simplified rate Eq. (A.10)
Initiator consumption rate. From material balances
on the initiator and the intermediates, we have: ½I0
ln ¼ k 1 K 0 ½LA0 t ðA:11Þ
½Iu;t
d½I
¼
k 0 ½I½LA þ k
0 ½I  LA ðA:1Þ This is equivalent to Eq. (6) in the text.
dt
Propagation rate. For Path A, the rate of propaga-
d½I  LA tion is described by Eq. (A.12):
¼ k 0 ½I½LA
k
0 ½I  LA
k 1 ½I  LA
dt
d½M
þ k
1 ½Iþ LA
 ðA:2Þ Rp ¼
¼ kp½Mð½Iþ LA
 þ ½Pþ

n LA Þ ðA:12Þ
dt
To obtain the net rate of consumption of both of these The consumption rate of the active propagating species
initiator-derived species together to form ionized species is given in Eq. (A.13):
12 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14

dð½Iþ LA
 þ ½Pþ

n LA Þ
½I þ ½Pn   ½I0 ðA:25Þ
¼ k 1 ½I  LA
k
1 ½Iþ LA

dt
þ k 1 ½Pn  LA
k
1 ½Pþ
½LA0
n LA  ½LA  ðA:26Þ
1 þ K 0 ½I0
ðA:13Þ

The combined change in initiator and polymer concen- With K0[I]0  1, [LA]  [LA]0.
trations with time can be written as follows: Substituting (A.25) and (A.26)into Eq. (A.20) gives
the general form of the differential polymerization rate
dð½I þ ½Pn Þ equation:
¼
k 0 ½I½LA þ k
0 ½I  LA
dt

k 0 ½Pn ½LA þ k
0 ½Pn  LA ðA:14Þ d½M ½I0 ½LA0
Rp ¼
¼ k p K 1 K 0 ½M ðA:27Þ
dt 1 þ K 0 ½LA0
Since the reactivities of the initiator and the growing
Assuming K0[LA]0  1 again, we can simplify and inte-
chains are about equal, the sums of the concentrations
grate the rate equation to get (A.28):
of the active cationic species and also the dormant spe-
cies are constant and the quasi-steady state assumption ½M0
ln ¼ k p K 0 K 1 ½I0 ½LA0 t ðA:28Þ
(QSSA) can be applied: ½M
dð½Iþ LA
 þ ½Pþ

n LA Þ (A.28) is equivalent to Eq. (7) in the text.
ffi0 ðA:15Þ
dt

dð½I þ ½Pn Þ Appendix B. Path B

ffi0 ðA:16Þ
dt
With this and assuming fast equilibria, the concentration Propagation rate. The rate of polymerization for Path
of active cationic species is derived as follows: B can be derived similarly to Path A:

½Iþ LA
 þ ½Pþ

n LA  ¼ K 1 ð½I  LA þ ½Pn  LAÞ ðA:17Þ d½M
Rp ¼
¼ k p ½Mð½Iþ LA
þ

2  þ ½Pn LA2 Þ ðB:1Þ
dt
½I  LA þ ½Pn  LA ¼ K 0 ð½I þ ½Pn Þ½LA ðA:18Þ
dð½Iþ LA
þ

2  þ ½Pn LA2 Þ
Substituting (A.18) into (A.17), we have ¼ k 2 ½I  LA½LA
dt
½Iþ LA
 þ ½Pþ

n LA  ¼ K 1 K 0 ð½I þ ½Pn Þ½LA ðA:19Þ
k
2 ½Iþ LA
2

where K1 = k1/k
1 and K0 = k0/k
0. þ k 2 ½Pn  LA½LA

Substituting (A.18) into (A.12) yields
k
2 ½Pþn LA2  ðB:2Þ
d½M
Rp ¼
¼ k p K 1 K 0 ½Mð½I þ ½Pn Þ½LA ðA:20Þ dð½I þ ½Pn Þ
dt ¼
k 0 ½I½LA þ k
0 ½I  LA
dt
Since the concentration of active cationic species
k 0 ½Pn ½LA þ k
0 ½Pn  LA ðB:3Þ
([I+LA
] and ½Pþ

n LA ) is very small, simplified mass
balances for the initiator and Lewis acid can be written dð½Iþ LA
þ

2  þ ½Pn LA2 Þ
as follows: ffi0 ðB:4Þ
dt
½I0 ¼ ½I þ ½Pn  þ ½I  LA þ ½Pn  LA ðA:21Þ
dð½I þ ½Pn Þ
ffi0 ðB:5Þ
½LA0 ¼ ½LA þ ½I  LA þ ½Pn  LA ðA:22Þ dt
Substituting (A.17) into (A.20) and (A.21) yields: Since the reactivities of the initiator and the polymer are
½I0 close to equivalent, the rate of consumption of the initi-
½I þ ½Pn  ¼ ðA:23Þ ating species is equal to the rate of the formation of the
1 þ K 0 ½LA
growing species.
and
½Iþ LA
þ

2  þ ½Pn LA2  ¼ K 2 ð½I  LA þ ½Pn  LAÞ½LA
½LA0 ðB:6Þ
½LA ¼ ðA:24Þ
½I0
1 þ K0
1 þ K 0 ½LA ½I  LA þ ½Pn  LA ¼ K 0 ð½I þ ½Pn Þ½LA ðB7 ¼ A7Þ

If the concentration of free Lewis acid is small, i.e., ½Iþ LA
þ
2

2  þ ½Pn LA2  ¼ K 2 K 0 ð½I þ ½Pn Þ½LA ðB:8Þ
K0[LA]  1, (A.23) and (A.24) can be simplified:
 J.E. Puskas et al. / European Polymer Journal 41 (2005) 1–14
where K2 = k2/k
2.
Substituting (B.8) into (B.1) yields:
d½M
Rp ¼
¼ k p K 1 K 0 ½Mð½I þ ½Pn Þ½LA2 ðB:9Þ
dt
The concentrations of the ionic species are very small,
thus the simplified mass balances established in Eqs.
(A.20) and (A.21) and Eqs. (A.22)–(A.25) will apply.
With these we get the form given below:
d½M ½I0 ½LA20
Rp ¼
¼ k p K 1 K 0 ½M ðB:10Þ
dt ð1 þ K 0 ½I0 Þ2
Assuming K0[LA]0  1 again and integrating, we get
(B.11):
½M0
ln ¼ k p K 0 K 1 ½I0 ½LA20 t ðB:11Þ
½M 2000;33:743.
Eq. (B.11) is equivalent to Eq. (9) in the text.
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