International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 19 (2016) pp.
9906-9913
© Research India Publications. http://www.ripublication.com
Low Density Polyethylene Tubular Reactor Modeling: Overview of the
Model Developments and Future Directions
A. Azmi
PG Scholar,
School of Chemical Engineering,
Universiti Sains Malaysia, Nibong Tebal,
14300, Penang, Malaysia
Abstract
Low-density polyethylene (LDPE) is one of the most widely used
polymers in the world. Commercially a very flexible and
branched LDPE is produced through free radical polymerization
of ethylene (monomer), in the presence of chemical initiators (i.e.,
peroxides, oxygen, azo compounds) in high pressure long tubular
reactor. A single polyolefin plant producing thirty to forty grades
of polymer, therefore understanding the reaction mechanism, the
operating variables as well as the dynamic behavior of tubular
reactor is essential. Furthermore, as the LDPE industry becomes
more competitive, manufacturers have to cope with growing
pressures for production cost reductions and more stringent
polymer quality requirements. To accomplish these goals, for the
past forty years numerous researchers had developed various
computational and mathematical models capable of monitoring,
predicting, optimizing and controlling the polymerization process
of polyethylene. The present paper provides an overview of the
model developments and its recent progress. It also addresses the
conceptual ideas for future improvement work in LDPE tubular
reactor modeling.
Keywords: Tubular reactor, LDPE, Polymerization, Modeling.
INTRODUCTION
Low-density polyethylene (LDPE) is one of the most important
polymers with great industrial significance. LDPE constitute large
number of applications including packaging, adhesives, coatings
and films. Being a commodity polymer, LDPE consumption
accounts for the 40% of worldwide polyethylene, which reached
over 35 million metric tonnes in 1994, and has been reported to
increase rapidly at the rate of 7% per year over the past 15 years
[1,2]. The exclusive properties of LDPE and its copolymers
indicate that the demand for these precious polymer grades will
remain enthralling in the near future. Driven by commercial
interest and improvement opportunity, numerous articles have
been published about its physical properties, reaction mechanisms
and process simulation and optimization.
A very flexible and branched LDPE, typically in the range of 910
– 940 kg/m3 manufactured commercially in a high-pressure free
radical polymerization reactors in the presence of a mixture of
initiators (e.g., peroxides, oxygen and azo compounds). Table 1
lists the property-ranges for commercial LDPE varieties.
Practically, almost all low-density polyethylene (LDPE) is
manufactured in stirred autoclaves or in tubular reactors at high
pressures. This paper focuses primarily on tubular reactor. The
high pressure tubular reactor is characterized by very large ratios
of length to diameter (L/D) ranging from 1 – 6 × 10-4. A typical
9906
N. Aziz,
Associate Professor,
School of Chemical Engineering,
Universiti Sains Malaysia, Nibong Tebal,
14300, Penang, Malaysia
high-pressure LDPE tubular reactor consists of a spiral-
wrapped jacketed metallic pipe with the total length of the
tube ranges from 500 to 1500 m arranged as a series of
straight sections connected by 180 degree bends, whereas the
inner diameter does not exceed 60-80 mm [1,3]. Wall
thickness equivalent to inner diameter is used to provide
necessary strength for the high-pressure involved in
polymerization of ethylene, typically at pressures of 101325
–303975 kPa and temperatures of 373.15 – 598.15 K [1].
Schematic diagram of an industrial LDPE tubular reactor is
shown in Figure 1. In Figure 1, TJin,n are the jacket inlet
temperature whereas TJout,n are referred as jacket outlet
temperature.
With regards to the process heat prerequisite, the
tubular reactor is segregated into a number of zones namely
preheating, reaction, and coolant zones. A typical commercial
tubular reactor usually comprise of 2 – 6 reactor zones and 6
– 12 coolant zones as shown in Figure 1, depends on the
reactor design and product specifications. In the initial zone,
Ethylene with other feed stream is heated (by steam or water)
up to the optimal temperature at which the polymerization is
initiated via the thermal decomposition of initiators. This
temperature relies on initiator utilized, ranging from 463.15
K for oxygen to 413.15 K for a peroxy-dicarbonate [4].
Ethylene polymerization is a highly exothermic reaction. The
heat generated during polymerization reaction is partially
removed through the reactor wall by the heat-transfer fluid,
which flows inside a reactor jacket. Almost half of the heat
generated via the reaction is removed by the cooling fluid
flowing in the reactor jacket co- or counter currently to the
reaction fluid [3].
Table 1. Properties of commercial LDPE [5]
Property Range
3
Density (kg/m ) 910 - 940
Melting temperature (K) 371.15 - 388.15
Melt flow index (g/10min.) 0.2-50
Tensile modulus (Mpa) 172.37 – 344.74
Tensile yield stress (Mpa) 8.96 – 19.31
The industrial significance of high-pressure LDPE tubular
reactor technology has led to extensive studies on reactor
modeling over the past 40 years. The most important goal of
the research is the maximization of the production
(maximization of the monomer conversion for a given feed
 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 19 (2016) pp. 9906-9913
© Research India Publications. http://www.ripublication.com

flow rate) and minimization of unwanted product (ethyl, butyl,
vinyl and vinylidene groups), while maintaining the
polymer product quality with regards to its molecular weight
distribution (MWD). The typical monomer conversions in tubular
reactor is reported to be vary in the range of 20-35% per pass
[3,4]. This paper presents the review of the model developments
and its recent progress in terms of reaction kinetics and reactor
modelling, simulation, and optimization.
REACTION MECHANISM AND KINETICS
A lot of extensive studies have been done on the reaction
mechanism and kinetics of free-radical ethylene
polymerization. The reaction mechanism applied give
significant effect to the reaction temperature profiles and
polymer properties. To date, no reaction mechanism is fixed
in the various literatures published. There are no mutual
agreement between authors to make the reaction mechanism
fixed for their modelling. The only reaction that is
completely acceptable for all authors are the main reaction of
free-radical polymerization which are initiation of free-
radicals, propagation and termination. In general, there are
more than 10 reaction mechanism (besides the main reaction)
available in the literatures in which researcher is open to
include or exclude in their model. Table 2 illustrate the
availability of particular reaction mechanism in several
papers available in the literature.

Fig.1. Schematic diagram of an industrial LDPE tubular reactor

[6]

Table 2. Summary of reaction mechanism availability in the recent publication.

Authors
Reaction mechanism
Asteasuain and Meimaroglou
Brandolin [7] et al. [26]
Main reaction:
Oxygen Initiation √ x
Peroxide Initiation (decomposition) √ √
Monomer thermal initiation √ x
Generation of inert √ x
Propagation √ √
Termination by Combination √ √
Termination by disproportionation x √
Termination by thermal degradation √ x
Side Reaction:
Chain transfer to polymer √ √
Chain transfer to monomer √ √
Chain transfer to solvent √ √
Backbiting √ √
β-Scission of secondary radical √ x
β-Scission of tertiary radical √ x
β-Scission or random scission x √
Disli and Erdeghem et al.
Kienle [29] [23]
x x
√ √
√ x
x x
√ √
√ √
√ √
x x
√ √
√ √
√ √
√ √
x x
x x
√ √

To date, reaction mechanism applied in Asetasuain and Brandolin
[7] can be considered as the most accomplish reaction
mechanism. Most of the reactions were selected after reviewing
the works by numerous publications
[8,9,10,11,12,13,14,15,16,17,18]. The generation of free radicals
is called initiation. Oxygen (O2) and organic peroxide (I)
initiation, and monomer (M) thermal initiationgenerate free
radicals when the reactor temperature reaches appropriate levels.
Peroxide initiation mechanism is unanimously accepted
among researchers in this field. However the latter initiation
mechanism which are oxygen and monomer thermal
initiation have thus fail to gain mutual agreement among
researchers. In the early LDPE industrial process, oxygen
was used as initiator due to its ease of feeding into the
reactor. However, as time pass by, through the developments
of high-pressure pumps and compressors, new plants employ

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 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 19 (2016) pp. 9906-9913
© Research India Publications. http://www.ripublication.com
solutions of liquid catalyst as initiator. A part from that, solutions
of liquid catalyst commonly organic peroxide help to ensure the
precise control of temperature profiles inside the reactor.
Some researchers [1,3,9,19,20,21,22,23] have neglected the
oxygen initiation mechanism due to the fact that the mechanism
by which oxygen generates the free radicals is complicated and
not well understood [4]. A part from that, it can acts as inhibitor
to radical polymerization at lower temperature. It reacts with
carbon radicals (both primary and chain), leads to the formation
of peroxy-radicals, which are relatively unreactive [24]. However,
Agrawal et al. [4] stated that oxygen is still widely used, either
alone or sometimes in combination with liquid initiators in the
tubular reactor process. The consideration of oxygen initiation
mechanism in Brandolin et al. [18] model is based on the works
by Tatsukami et al. [11], Hollard and Ehlrich [12] and Brandolin
[13]. In general, at low concentration, oxygen may act as an
indirect initiator, where oxygen first reacts with monomer to form
peroxides. These peroxides then decompose and actively react
with monomer to generate chain radicals which initiate the
polymerization [24]. Tatsukami et al. [11] postulated the reactions
which account for initiation and inhibition effects of oxygen
would help to predict the shape of the temperature profile at the
peak and therefore increase the accuracy of the model.
Kim and Iedema [21] have removed monomer thermal initiation
due to the fact that the reaction is a slow third order reaction in
the absence of initiators thus it is negligible in their modelling.
Other authors [9,13,23,25,26] removed it from their model due to
simplification purpose. However, Asteasuain et al. [27] stressed
that monomer thermal initiation must necessarily be kept in
reaction mechanism because it becomes important at runaway
conditions in the tubular reactor, which occurs at higher
temperature. The free radicals react with monomer to produce a
growing macromolecule during propagation and increase the
chain length. This macro radicals may be deactivated by oxygen,
generating an inert. Asteausuain and Brandolin [7] stressed the
significance of this reaction in order to obtain an accurate
prediction of temperature peaks. Natural termination is obtained
by combination of growing radicals react with each other and
form dead polymers or via thermal degradation. Ehrlich and
Mortimer [8], Chen et al. [9] and Brandolin et al. [13] reject the
idea to include mutual chain termination by disproportionation in
their model since they identify that the inclusion of this reaction
will serve no purpose.
Chain transfer to monomer and polymer, and the use of non-
saturated solvents (S) such as propylene, allows for the generation
of polymer and initiation radicals possessing terminal double
bonds. Such form may propagate and favor the long chain
branching occurrence [18]. Adding transfer agents or solvents (S)
to the tubular reactor help to control the molecular weight, since
they react with radicals producing a dead polymer and initiation
radical. Such reactions occur through hydrogen abstraction and
consequently lead to shorter macromolecules. Transfer to
monomer and polymer are also crucial for the prediction of the
molecular weights. Agrawal et al. [4] stated in their paper that
chain transfer to monomer is small in case of ethylene and the
reaction is quite similar to other monomer systems as well. In
case of chain transfer to polymer, Pladis and Kiparissides [28]
concluded that it is the primary reaction in the formation of long
chain branches (LCB). In high pressure ethylene polymerization,
these branches widen the molecular weight distribution of LDPE.
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Thus far, almost all researchers have included this
mechanism (chain transfer to monomer, polymer and solvent)
in their model except few, notably Chen et al. [9] due to
model simplification purpose.
Backbiting reaction and scission reactions is the major source
of short chain branching (SCB) in LDPE and they were
selected after reviewing the works of Goto et al. [11]. The
backbiting reaction, occurs when the carbon atom preceded
by four carbons back down the chain. Agrawal et al. [4]
conclude that these branches contain entirely ethyl- and
butyl- groups. β-Scission of secondary and tertiary radical
allow the independent estimation of the short chain branching
such as vinyl and vinylidene groups. Nevertheless, for
several authors [23,26,29], they considered the scission
reaction to be in random, rather than separately as was used
in Asetasuain and Brandolin [7]. Selection of reaction
mechanisms plays significant role to develop an accomplish
model with highest accuracy. However, depending on the
degree and complexity of the research scope, one has the
options of including or excluding the reaction mechanism
component in their model based on the justification
mentioned in literatures.
MODELLING, SIMULATION AND OPTIMIZATION
Extensive workers (engineers, researchers and chemist) have
sought to model the high pressure low density LDPE tubular
reactor over the past few decades. However, even with the
extensive works of research, complete understanding of the
physico-chemical phenomena occurring inside such reactors
still remains elusive. This section review some of the
previous study carried out by previous researchers. A
complete review of all research is extremely huge and
beyond our capability and we have attempted here to
highlight key efforts relevant to LDPE study. A
comprehensive study has been carried out on modeling of
LDPE process [1,4,7,9,10,16,18,23,30,31,32,33]
In most of the studies, homogeneous phase (single phase) of
ethylene and polyethylene is assumed. Ehrlich and Mortimer
[8] studied the phase-equlibria and the elementary reactions
involved in the free-radical polymerization of ethylene. One
of the important findings of their research is that, at typical
temperatures and pressures encountered in commercial
polymerization processes, the monomer and polymer, form
and exists as a single fluid phase. This fact has been used in
many subsequent modeling studies. Further study by Buback
[16] in an extended pressure and temperature region above
150 Mpa and 423.15 K, reveal that the reaction mixture
inside reactor exists as single phase respectively. Following
this Zabisky et al. [32] used this assumption on their terminal
model for copolymerization.
Agrawal and Han [30] performed a modelling study with
axial mixing to determine its effect on the LDPE tubular
reactor performance. This research was the first of its kind
since earlier efforts at modeling LDPE tubular reactors have
considered plug-flow in their models. They stressed that axial
mixing in such reactors is of significance due to the pulse
valve effect inside the tubular reactor. Latter study carried by
Chen et al. [9] which utilized on a simplified plug-flow
 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 19 (2016) pp. 9906-9913
© Research India Publications. http://www.ripublication.com

Table 3. Rate constant from different researchers

Rate Chen et al. [9] Mavridis and Kiparissides Brandolin et al. [18]
constant [36]
A (1/s) E (kJ/mol) A (1/s) E (kJ/mol) A (1/s) E (kJ/mol)
1.60E16 160.66 2.50E14 125.52 1.1E10 – 8.7E17 94.56 – 133.05
- - 5.93E18 195.21 1.1E10 – 3.2E13 94.56 – 132.63
- - - - (1.60 ± 0.0010)E11 135.85 ± 0.02
- - - - - -
2.95E7 29.67 1.25E8 31.04 (4.0 ± 0.0110)E5 17.61 ± 0.003
1.60e9 10.04 2.50E9 4.18 (8.7 ± 0.0130)E8 15.27 ± 0.003
- - 2.50E9 4.18 - -
2.72E11 83.68 - - - -
- - 1.25E6 45.35 (1.2 ± 0.0001)E5 60.25 ± 0.004
9.00E5 37.66 1.24E6 30.33 (7.6 ± 0.0006)E9 79.91 ± 0.006
- - 2.75E7 43.39 4.6E6 – 9.9E7 33.05 – 46.86
- - - - (1.2 ± 0.0002)E10 61.92 ± 0.004
- - - - (1.4 ± 0.0001)E9 79.91 ± 0.004
- - - - (4.4 ± 0.0005)E9 79.91 ± 0.004
- - 6.07E7 45.19 - -

Rate Dhib and Al-Nidawy [37] Yao et al. [1] Agrawal et al. [4]
constant
A (1/s) E (kJ/mol) A (1/s) E (kJ/mol) A (1/s) E (kJ/mol)
1.81E16 177.02 2.29E14 126.05 1.00E14 119.85
6.04E13 175.49 - - 1.00E12 123.03
- - - - 1.6E11 132.08
6.04E3 305.20 6.04E3 305.17 - -
5.45E5 17.61 9.90E5 17.61 4.00E5 17.42
4.35E8 15.27 4.35E8 15.27 8.70E8 15.27
- - 3.25E8 1.01 - -
- - - - 7.70E9 79.91
1.20E5 60.25 1.2E5 60.24 - -
1.80E8 39.32 1.8E8 39.33 5.20E4 36.82
- - 5.60E7 41.97 7.00E4 18.39
3.25E5 31.27 - - 1.20E10 60.50
1.40E9 80.75 1.40E9 79.91 1.40E9 84.69
- - 4.40E9 79.91 4.40E9 70.16
- - - - - -

model showed that axial mixing can be neglected for all practical
purposes using the same reactor system of Agrawal and Han [30].
Furthermore, Donati et al. [34] and Yoon and Rhee [31] also
remarked that axial mixing contribute insignificant effect on the
reactor performance and therefore can be neglected under typical
industrial operating conditions. Therefore, most of the studies
conducted later on by numerous researchers eliminate axial
mixing assumption from their model.
An overview of information on modelling studies on
LDPE reactors available in the open literature indicates
significant discrepancies among researchers for kinetic
constants as summarized in Table 3. Brandolin et al. [13]
attempted to establish reliable kinetic data which utilized the

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 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 19 (2016) pp. 9906-9913
© Research India Publications. http://www.ripublication.com
initiation by oxygen, propagation, and termination by
combination, thermal degradation and chain-transfer reaction
mechanism. The authors determined the kinetic rate parameters
using a non-linear regression analysis of data obtained from two
different reactor configurations with regards to their temperature
profile and molecular properties. The model was able to predict
reactor states and product properties. Following this, Brandolin et
al. [18] extended their previous model by incorporating realistic
features such as multiple initiator injections and included typical
heat-transfer coefficients obtained from plant data. However, they
showed the kinetic rate parameters for initiators and telogen in a
range due to maintain confidentiality of their work. Same
procedure was repeated by Zabisky et al. [32] as they also did not
provide the kinetic rate parameters obtained after validation of
model to industrial data due to proprietary reasons. Agrawal et al.
[4] gave the tuned kinetic rate constant values in their paper.
Their model were based from Asteasuain et al. [35], which
provide the design features, steady-state operating conditions,
measured temperature profile along the reactor length, monomer
conversion and number-average molecular weight at reactor exit.
Agrawal et al. [4] have included chain transfer to polymer, β-
scission of secondary radical and tertiary radical reactions to the
original kinetic scheme used by Asteasuain et al. [35]. Physical
properties and pressure variations along the axial length included
are their new contribution to the Asteasuain
et al. [35] model. However, Agrawal et al. [4] neglect some of the
reaction mechanism notably monomer thermal initiation,
termination by disproportionation and generation of inert.
According to Ray and Laurence [38], molecular weight
distribution (MWD) of the polymer plays significant role in
determining the polymer quality. As a consequence, a principal
theme in all modelling efforts in LDPE manufacturing is directed
towards MWD of the polymer. Hulburt and Katz [39] proposed
the method of moments in their study. Although their primary
focus was on nucleation and growth kinetics commonly
encountered in crystal growth studies, they realised that their
approach could be easily extended to include other kinds of
"particles". In term of LDPE production that term of “particles”
would mean the free-radical polymerization. A method of
moments for polymer size distribution in time was studied
rigorously by Katz and Seidel [40]. They considered basic
reaction of initiation, propagation and termination by combination
in their kinetic mechanism. One of the most important discovery
of their research is that monomer conversion and polymer size
distribution was controlled by a suitable defined dimensionless
group. The authors also highlighted the effect of inclusion of
chain transfer and termination by disproportionation in reaction
mechanism. Seidel and Katz [41] continued the study by
describing a dynamic analysis of branching in free-radical
polymerization in terms of the moments of the polymer size
distributions, the mean number of branches and the rate of
polymerization. An important findings of this study was that
chain-transfer reactions have significant effect of widening the
final product MWD. This findings has been used in many
subsequent LDPE polymerization modeling studies.
Extensive research to determine the fouling inside
tubular reactor was done by Buchelli et al. [42]. They had used
the heat transfer model and industrial data to calculate the fouling
thickness and fouling deposition rate over time. The authors
concluded that fouling in a reactor was caused by a tiny fraction
9910
of precipitated gets attached to reactor inner wall. In the
following study, Buchelli et al. [43] used computational fluid
dynamic (CFD) simulation to investigate the effect of fouling
on reactor temperature, polymer properties and monomer
conversion. However, their prediction of reactor wall inside
temperature was contradict to observed temperature in the
real plant. This should act as impetus for the future researcher
to study the fouling effect since it may lead to runaway
condition in LDPE tubular reactor.
Several studies on the optimization of LDPE are
available in the literatures. Yoon and Rhee [31] focus on the
maximization of monomer conversion as their objective
function. However, the authors did not highlight the polymer
quality (through MWD) in their study. Mavridis and
Kiparissides [36] derived a general mathematical model that
maximized the reactor productivity while maintaining the
product quality in terms of monomer conversion and the
moments of MWD. Important conclusion of their work and
used in the subsequent study is polymer with specified
molecular weight characteristics is obtainable through proper
manipulation of the control variables. Nevertheless, their
work was rather too general and some of the reaction kinetics
was missing from their model. Kiparissides et al. [44]
developed an on-line multi-level optimization based on a
steady state model. They include parameter estimation in
their study and considered ethylene conversion and product
quality as their objective function.
Cervantes et al. [45] used a simplified nonlinear
model to obtain optimal switching time between different
steady states (correspond to two different polymer grades)
with a feed mixture of ethylene, methane, butane and
impurities. Asteasuain et al. [27] attempted a study optimal
start-up policies of LDPE reactor. Maximization outlet
conversion and the product quality are their objective
function while feed flow rates of initiators and telogens are
used as decision variables. However, the authors did not
include shutdown strategies in their optimization study. Yao
et al. [1] applied genetic algorithm to obtain the optimal
jacket temperature profile required to maximize the polymer
productivity. Their model include focus on the utilization of
reactor length, and observed that conversion as high as
42.33% (highest than any reported previously) is obtainable
through the implementation of 5 initiator injections.
Nevertheless, their work is not validated with any of the
experimental or industrial data.
Agrawal et al. [4] focus on maximization of
monomer conversion and minimization of undesirable side
products using binary coded non-dominated sorting genetic
algorithm and jumping gene adaptations. Their work was
based on the dynamic model by Asteasuain et al. [35], with
various modification and additional of kinetic mechanism
taking place. Zavala and Biegler [22] derive a general
nonlinear model predictive control (NMPC) with the
integration of moving horizon estimation (MHE) strategies to
optimize the operation of LDPE tubular reactors. Their
tracking NMPC controller is able to stabilize the reactor in
the case of persistent fouling disturbances. Erdeghem at al.
[46] works are more towards profit oriented. The first study
was more focusing on maximize the LDPE productivity
while minimizing the investment cost. Their pareto optimal
 International Journal of Applied Engineering Research ISSN 0973-4562 Volume 11, Number 19 (2016) pp. 9906-9913
© Research India Publications. http://www.ripublication.com
study of multi-peak models was able to identify where along the
tubular reactor and how much amount of initiator has to be
injected to maximize the profit at different economic situations.
Their subsequent study was to identify the most optimum reactor
configuration. A short cold cooling zone in the first and last peak
and longer cooling zones in the second and third peak was
observed to be the most optimum reactor.
CONCLUSION
Although numerous efforts directed towards a realistic model
development and improvement are abundant in the literatures,
there exist a large space of area for further analysis and
improvement in the LDPE tubular reactor polymerization. In term
of the reaction kinetic, there exist a significant discrepancies of
kinetic constant rate among researchers. It was proven that kinetic
constant are determinant of temperature and conversion profile,
thus efforts towards a realistic model for high pressure tubular
reactor have to deal with the lack of consistency of kinetic
information in the open literature. Thus, determining the reliable
kinetic constant to a model will always remain as a challenge to
researcher.
For reaction modelling, simulation and optimization, the fact that
large area in LDPE tubular reactor polymerization are covered or
at least discuss by researcher is undeniable, however some area
are still left untouched or may be need some in depth study. For
instance, variation in number of tubular reactor zone was not
highlighted properly by any of the researcher. Its importance also
is not addressed elsewhere in the literatures. In terms of
optimization, various of research were using steady state model.
An integration of optimization technique to a comprehensive
dynamic model can be fruitful to the study.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge the financial support given
by Universiti Sains Malaysia through Research University Grant
No. 1001/PJKIMIA/814237 and Malaysian government through
MyBrain 15 funding.
Nomenclature
A Frequency factor
E Activation energy
∆V Activation volume
fo Efficiency of inert generation by oxygen
Im mth fictitious peroxide initiator, (k= 1, 2, …)
km,x xth Peroxide initiation rate constant
ko Initiation by oxygen rate constant
kth Monomer thermal initiation rate constant
kp Propagation rate constant
ktc Termination by combination rate constant
ktdt Thermal degradation rate constant
ktrm Transfer to monomer rate constant
ktrp Transfer to polymer rate constant
ktrs Transfer to transfer agent rate constant
kbb Back-biting rate constant
kβ1 Secondary radical b-scission rate constant
kβ Tertiary radical b-scission rate constant
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M Ethylene monomer
O2 Oxygen
P(m) Polymer molecule of chain length m, (m= 1, ..., )
P Reactor pressure
R(m) Living radical of chain length m, (m= 0, ..., )
S Fictitious transfer agent
TJ Jacket temperature
X Inert molecule.
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