A Study of the Gas Phase Polymerization of Propylene: The impact of catalyst

treatment, inject conditions and the presence of alkanes on polymerization and polymer
properties.

Ana R. Martins1,2, Aarón J. Cancelas1, Maria R. Ribeiro2, Timothy F. L. McKenna1

1
Laboratoire de Chimie, Catalyse, Polymères et Procédés (C2P2), LCPP Group, Villeurbanne, France

2
Departament of Chemical Engineering, Instituto Superior Técnico, Lisbon, Portugal

ABSTRACT: The effect of changing reaction It is also observed polymerization rate is higher
conditions on propylene polymerization using a when the catalyst is pre-contacted with a liquid
Ziegler-Natta catalyst is studied. It is observed that hydrocarbon instead of injecting it dry.
the instantaneous rate of polymerization increases
performing a prepolymerization. This is attributed The presence of an alkane increases the rate of
to the effect of prepolymerization step in decreasing polymerization, by the absorption of the reaction
local particle overheating in the initial instants of heat by its latent heat of vaporization but also by
reaction, due to a lower catalyst activity. enhancing the local concentration of propylene
inside the active sites.
Hydrogen concentration affects the instantaneous
rate of polymerization, once it reactivates dormant Keywords: propylene, prepolymerization, dry
sites of the catalyst. A lower rate is observed in the injection, wet injection, hydrogen concentration,
absence of hydrogen, since there are less active alkane, turbosphere reactor.
sites where polymerization reaction can occur.

INTRODUCTION: Polypropylene is one of the can have an effect on the heat removal and the
most important polyolefins along with polyethylene deactivation of the catalyst.
and is one of the most versatile thermoplastic
polymers available. It is widely used thanks to its It has already been studied that performing a
properties, which include low density, high prepolymerization step before the main
stiffness, heat resistance, recyclability, easy to polymerization reaction can significantly help
weld, etc, making it one of the most produced controlling the growth of the polymer particle and
polymers in the world, with a production exceeding avoiding the overheating of the particles during the
50 Mton per year. initial reaction times, when catalyst is highly
activated.[1],[2] The prepolymerization must occur at
Despite the already massive market for polyolefins mild conditions, which allows the crystal fragments
(estimated to be 125 million tons in 2011), its to be separated and covered by a thin layer of
global consumption is expected to grow over the prepolymer. These mild conditions are responsible
next years, continuing holding a major portion of for the production of the regular fragments’ size
the market share of the commodity plastics and better replication of the catalyst shape.
globally. Due to the expected growth of
consumption, there is a need to increase the The injection of an alkane, to the best of our
productivity and space-time yield in existing knowledge, it has not ever been made during
processes; making them able to have a bigger propylene polymerization. An induced condensing
production to satisfy its consumption. agent (ICA) is a saturated alkane normally between
4 and 6 carbon atoms in its structure, introduced in
As it is known, olefin polymerization reactions are the beginning of olefin polymerization. Using this
highly exothermic, what makes heat removal one of type of approach it is possible to increase the rate of
the main limitations to achieve higher production heat removal in polyolefin processes. By the
rates. Gas phase processes are even more affected vaporization of the liquid alkane, a high amount of
by this, given the known limitations of heat transfer heat can be removed thanks to its latent heat of
in gas state. In the current paper, will be studied the vaporization.
impact of changing some reaction conditions that
In ethylene polymerization, Alizadeh and In the current paper, kinetic profiles and powder
Namkajorn observed that the instantaneous rate of characterization obtained from gas phase semibatch
ethylene polymerization is promoted when a higher polymerization reactions have been compared using
amount of ICA is introduced [3]. different reaction conditions such as
prepolymerization step, hydrogen concentration,
In other hand, the presence of a vaporized alkane catalyst injection and condensed mode cooling
can modify the way the reaction proceeds. This is using a commercial Ziegler-Natta catalyst.
caused by the co-solubility effect: the presence of
an alkane will provoke an increase of the diffusivity Experimental Section
of ethylene, boosting its concentration inside the
active sites of the catalyst, increasing the reaction Chemicals
rate. It is also true that more the alkane is soluble in
the polymer, greater is the observed effect. The precatalyst was a commercial MgCl2 supported
TiCl4 fourth generation Ziegler Natta, with titanium
In propylene polymerization, propylene is fed content 2.8% and with di-isobutyl phtalate as
partially liquid and by its vaporization it will internal donor. The catalyst had a wide particle size
remove the reaction heat itself, not being necessary distribution and an average size of about 10,6 µm.
a different induced condensing agent to remove
heat. On the other hand, the presence of an alkane Tryethylaluminum (TEA) used as cocatalyst and
will affect the activity, increasing it by the scavenger in 1M dilution in heptane was purchased
enhancement of local concentration of propylene from Witco, Germany. Dicyclopentyl dimethoxy
inside the active sites. silane (DCPDMS) was used as external electron
donor, in 0,42M solution with heptane. The catalyst
Another important aspect in olefin polymerization injection was made in two different ways: Sodium
is the presence of hydrogen in the reaction medium Chloride (Acros Organics France) with purity of
because it plays a decisive role in the way the 99,5% and mineral oil (OIL PRIMOL 352). TEA
reaction proceeds. Mori et al.[4] studied the effect of (1M, heptane solution) was used in a ratio of 190
hydrogen in slurry polymerization and concluded Al/Ti and the external Lewis base used in a 10 Si/Ti
that it acts as a chain transfer agent and increases ratio.
activity, since it has the capacity of reactivating
dormant sites. The salt was previously vacuum-dried during five
hours at 200ºC and kept under argon atmosphere at
As it is known Ziegler-Natta catalysts produce room temperature. The oil was degassed frozen
polymers with high regioregularity[5], favoring 1-2 under vacuum and then kept under argon. The
insertions and head-to-tail enchainment. If the experiments performed with dry injection were
insertion of the polymer is from 2-1 or with other made with 30 mg of ZN catalyst, injected along
enchainment, it will affect the melting point and the with 10 g of salt. The wet injection was made
crystallinity of the polymer, as well as the activity, injecting 250 μL of oil, which cores 15 mg of ZN
since these can also block active sites. Having this catalyst.
type of regioregularity problem, the active site of
the catalyst will stay dormant, which can be The propylene used was obtained from Scott
reactivated by the hydrogen. Specialty Gases with a purity of 99,95% and passed
through a three stage system of columns before use:
Several patents show that adding a small amount of a first one filled with BASF R3-16 catalyst (CuO
hydrocarbon to the catalyst prior to its injection in on alumina), a second one filled with molecular
the reactor can help polymer production. As a way sieves (13X, 3 Å, Sigma-Aldrich) and a last one
of testing the influence of catalyst injection, two filled with Selexsorb COS (Alcoa). Hydrogen with
systems were studied: solid-solid with salt and minimum purity of 99,9% were purchased from Air
solid-liquid with mineral oil. In both cases, the Liquide (France) and used as received. Argon
suspension media can absorb some of the reaction provided by Air Liquide, France, with minimum
heat, improving heat transfer between catalyst purity of 99,5%, was used in order to keep the
particles and surrounding environment. In the case reaction environment free of oxygen. Heptane, pre-
of wet injection, the oil can also fill the catalyst’s treated on 3 Å molecular sieves, was used for
pores, slowing the diffusion of monomer to the preparation of cocatalyst and external donor
active sites, acting like the prepolymerization step solutions.
in each pore of the catalyst. After some moments of
reaction, this liquid either evaporates or is displaced The alkane used in this work was iso-hexane from
from the pores, which enables the monomer to enter Sigma-Aldrich with a minimum purity 99%,
freely in the active sites. previously degassed frozen under vacuum and then
kept under argon.
Polymerization Methods to the reactor and agitation (300 rpm) was started.
Subsequently, about 5 minutes after the first
Gas phase homopolymerizations were done in a injection the donor/heptane mixture and the catalyst
2,5L semibatch reactor with injection valves for the suspension were injected under an argon stream.
catalyst and monomer feeds. The system was kept Finally the reactor is pressurized with a mixture of
under isothermal conditions and constant agitation monomer-hydrogen in the desired ratio.
of 300 rpm Reactor system is schematically shown
in Figure 1. Note that propylene polymerizations were
performed using 15-30 mg of precatalyst. TEA and
DCPDMS amounts were fixed to keep the Al/Ti
ratio close to 190 and the Si/Ti ratio close to 10.

Once the reaction is finished (normally one hour)

the monomer inlet is closed and the reactor is
rapidly cooled down and depressurized. Polymer is
recovered either directly from the reactor in the
mineral oil injection case, either after washing it
with demineralized water, to dissolve NaCl. In this
last case the final powder is then dried for at least
one hour at 90 ºC to remove the remaining traces of
solvent.

Prepolymerization Procedure
Figure 1 – Polymerization setup represented
schematically. Gas phase prepolymerization was performed at
3,5 bar of propylene pressure, without hydrogen, at
(1:Propylene Reservoir; 2:Propylene Purification 40 ºC during 10 min. Then temperature and
Columns; 3:Experimental Propylene Ballast; pressure were gradually increased at full reaction
4:Reactor Agitation Controller; 5:Catalyst Cartridge conditions over the course of approximately
Injector; 6:Gas Phase Reactor; 7:Data Processor; 20 min. Thus, an isothermal/non-isothermal
8:Heated Water Bath; 9:Hydrogen Ballast; prepolymerization method is applied (INM) [1]. The
10:Liquids Injection Valve) prepolymerization rate profiles are not shown, but
the yields were always approximately 200 g g-1.
Reaction Preparation Powder Characterization
Precatalyst Preparation Bulk Density
Regardless of the method of injection, the The bulk density was determined a defined volume
precatalyst was prepared in a glovebox (Jacomex, of propylene. The recipient was firstly filler with
France) under argon atmosphere. Oil suspended water and weighted to know its exact volume. The
precatalyst was kept on suspension by permanently bulk density is indicated in gram of polymer per
agitation, and a micropipette was used to take the liter.
required volume and inject it into the turbosphere.
For the solid suspension system precatalyst was Differential Scanning Calorimetry
diluted with coarse salt in a 100 cm3 cartridge
injector. The precatalyst was not pre-activated The crystallinity and melting point was analyzed in
before injection to the turbosphere reactor. a Differential Scanning Calorimeter from Mettler
Toledo. During this analysis, each polymer sample
Reactor Preparation is individually cooled until it reaches -80°C, then it
is heated to 200°C, followed by a decrease until
To purify the turbosphere reactor, it was heated up -80°Cand a second heat step to 200°C.
to polymerization temperature before the reaction
started, filled with argon and then under vacuum for Size Exclusion Chromatography
30 min. The cycle is repeated three times in order to
minimize the quantity of impurities remaining in The molecular weight distribution was analyzed in
the reactor. high temperature size exclusion chromatography
equipment. The samples were dissolved in
Polymerization Procedure trichlorobenzene and left heating and agitating for
one hour and a half. After this time, each sample
After the system had reached the desired initial was passed by the three columns inside the
temperature, the TEA/heptane mixture was injected equipment.
Results and Discussion The name of the experiments in generally given by
TXX-Y-Z% where XX is 40 in case of
The instantaneous rate of propylene polymerization prepolymerization is performed and 70 if not
is calculated from the rate of pressure drop in the (except in the case of dry injection); Y is the
propylene feed ballast. To ensure that the results quantity of alkane used in terms of the saturation
were reproducible, all polymerizations were point used (0, 25, 50, 75 and 100%); and finally, Z
repeated at least twice under a given set of is the concentration of hydrogen.
operating conditions. The list of experiments
performed in the current study is summarized in Influence of prepolymerization
Table 1.
The effect of a prepolymerization step is shown in
Table 1 - Reaction conditions used in each run. Figure 2 where I can be seen that over the course of
one hour the activity is higher the one obtained by
Alkane Cat. H2 direct polymerization. As we can see below there is
Run Prep. a boost in the rate of reaction when
(bar) Inj. (%)
prepolymerization is performed which is due to a
T40-0-2% YES 0 WET 2
higher catalyst activity, caused by the gradual
T40-25-2% YES 0,33 WET 2
increase of the particle surface area at a low
T40-50-2% YES 0,67 WET 2 reaction rate in the first moments of the
T40-75-2% YES 1,00 WET 2 polypropylene formation. Since it occurs in a lower
T40-100-2% YES 1,33 WET 2 reaction rate, there is less heat of reaction generated
T70-0-2% NO 0 WET 2 resulting in less deactivation of the catalyst
T70-25-2% NO 0,33 WET 2 particles.
T70-50-2% NO 0,67 WET 2
T70-75-2% NO 1,00 WET 2 At the beginning of the polymerization reaction, a
T70-100-2% NO 1,33 WET 2 high catalytic activity can lead to a rapid
T40-0-0% YES 0 WET 0 temperature increase of the catalyst particle. Owing
T40-100-0% YES 1,33 WET 0 to the small surface area and to difficulties on heat
T40-0-1% YES 0 WET 1 transfer between particle and reaction environment,
T40-100-1% YES 1,33 WET 1 there is an uncontrolled fragmentation of the
T40-0-4% YES 0 WET 4 catalyst particle, destroying it [2] and leading to a
T40-100-4% YES 1,33 WET 4 polymer with lots of fines. When using a
TDry-0-2% YES 0 DRY 2 prepolymerization technique before the
TDry-100-2% YES 1,33 DRY 2 polymerization itself, the catalyst surface area is
gradually increased at a low reaction rate [1], which
improves the heat transfer and leads to a better
polymer particle formation and catalyst replication.

9 T40-0-2% T70-0-2%
7,5
Activity (kg/g/h)

4,5

1,5

0
0 10 20 30 40 50 60
Time (min)
Figure 2 - Kinetic profiles of reactions with and without performance of prepolymerization step.
Type of catalyst injection The type of catalyst injection can affect severely the
activity of the polymerization reaction and also the
Since the quantity of catalyst injected is in the order morphology of the polymer. As we can see in
of milligrams, its injection has to occur in a Figure 3, the activity decreases to the lowest values
suspension media. Two ways of doing it were when catalyst injection is made in dry.
studied: dry injection and wet injection.

9 T40-0-2% T40-100-2%
7,5 TDry-0-2% TDry-100-2%
Activity (kg/g/h)

4,5

1,5

0
0 10 20 30 40 50 60
Time (min)

Figure 3 - Kinetic profiles using different type of catalyst injection.

In dry injections there is no resistance to the arrival resulting in a high amount of heat produced leading
of monomer to the active sites during the initial consequently to quick catalyst deactivation. There
instants that follow catalyst injection into the are also some studies which show that adding a
reactor. This most likely provokes a higher initial small amount of inert liquid hydrocarbon before
reaction rate, with its subsequent overheating due to catalyst injection helps polymer production.
exothermic reaction.
Hydrogen Concentration
Even when injecting an alkane, the activity does not
increase as it was expected. Since the alkane is Figure 4 and 5 shows the difference of introducing
introduced after the prepolymerization and even in the reactor different amounts of hydrogen and
with mild conditions during this step, the salt does also how the injection of alkane effects it.
not have the same capability that oil has to retard
the diffusion of monomer into the active sites,

9 T40-0-0% T40-0-1%

7,5 T40-0-2% T40-0-4%

6
Activity (kg/g/h)

4,5

1,5

0
0 10 20 30 40 50 60
Time (min)

Figure 4 - Kinetic profile using different amounts of H2: 0, 1, 2 and 4% in the absence of alkane.
 9
T40-100-0% T40-100-1%
7,5
T40-100-2% T40-100-4%
6
Acitivity (kg/g/h)

4,5

1,5

0
0 10 20 30 40 50 60
Time (min)

Figure 5 - Kinetic profile using different amounts of H2: 0, 1, 2 and 4% in the presence of alkane.

Looking at the previous profiles, it is possible to Presence of alkanes

notice the rise of activity with the increasing
concentration of hydrogen. As hydrogen has the The quantity of alkane introduced in the reactor was
function of reactivating dormant sites, it is expected calculated in order to achieve the dew point of the
that the activity will increase with a higher mixture. After knowing that value, experiments
concentration of H2. The injection of alkane were done using fractions of it, like 25, 50, 75 and
amplifies even more this difference, since it does 100%. In Figure 6 it is possible to analyze the
not just enhances the local concentration of influence of feeding different amounts of alkane to
propylene inside the active sites but also the use of the reactor, when there is no performance of a
hydrogen, which will boost the activation of prepolymerization step. Figure 7 represents the
dormant sites. influence of the amount of alkane fed to the reactor
in rate of activity, when a prepolymerization step is
After 2% hydrogen, reaction activity does not performed.
change significantly with the increase of hydrogen
concentration. This conclusion is supported in both
cases, with alkane injection or without. One
experiment was also performed with 10% H2
resulting in no activity.

T70-0-2% T70-25-2% T70-50-2%

9
T70-75-2% T70-100-2%
7,5
Activity (kg/g/h)

4,5

1,5

0
0 10 20 30 40 50 60
Time (min)

Figure 6 - Kinetic profile using different amounts of alkane without prepolymerization step.
 T40-0-2% T40-25-2%
9
T40-50-2% T40-75-2%
7,5 T40-100-2%
Activity (kg/g/h)

4,5

1,5

0
0 10 20 30 40 50 60
Time (min)

Figure 7 - Kinetic profile using different amounts of alkane with prepolymerization step.

It is possible to conclude from the previous figures temperature, triggered by the exothermicity of the
that the activity rate increases with the amount of polymerization reaction.
alkane introduced in the reactor. This is due to two
main reasons: heat removal and co-solubility effect. Molecular Weight Distribution
The injection of a liquid compound in the reactor
can increase the amount of heat removal in Table 2 shows the variation of Mw and Mn with the
polyolefins processes, since it can absorb heat different reaction conditions studies.
thanks to its latent heat of vaporization. In other
hand the co-solubility effect is another reason for Table 2 - Molecular weight distribution of samples analyzed.
the increase of activity. The presence of an alkane
increases the solubility of smaller molecules inside RUN MN (kDa) MW (kDa)
the active sites of the catalyst. In other words, the T40-0-2% 41 / 58 270 / 284
presence of an alkane can enhance the local T40-25-2% 33 / 54 301 / 298
concentration of propylene inside the active sites of T40-50-2% 25 / 80 296 /336
the catalyst, resulting in a higher reaction activity. T40-75-2% 77 / 71 287 / 280
T40-100-2% 50 / 51 287 / 280
Comparing profiles with the different amount of T70-0-2% 49 / 53 275 / 258
alkane it is possible to conclude that the T70-25-2% 30 / 31 289 / 283
introduction of 75% of the quantity of the dew T70-50-2% 72 / 70 295 / 313
point seems to lead to same kinetic profile as the T70-75-2% 59 / 71 247 / 307
total quantity of the dew point. This happens in T70-100-2% 60 / 76 301 / 305
both cases, with and without prepolymerization. T40-0-0% 45 / 93 539 / 541
T40-100-0% 32 / 40 366 / 345
The difference between kinetic profiles with T40-0-1% 27 / 35 227 / 254
distinct amounts of iso-hexane is even more evident
T40-100-1% 951 5801
when prepolymerization is performed. This happens
T40-0-4% 55 / 53 287 / 313
because prepolymerization helps enlarging the
T40-100-4% 30 / 31 292 / 285
particle surface area, what leads to higher local
concentration of propylene enlarged even more due TDry-0-2% 42 / 55 233 / 247
to the co-solubility effect. Combining the presence TDry-100-2% 30 / 40 102 / 114
1 – Only one sample analyzed.
of an alkane and prepolymerization seems to lead to
the highest activity profiles.
Concerning the amount of alkane introduced it is
Finally, it is possible to conclude that when there is possible to conclude that it does not affect MWD,
no prepolymerization, the deactivation is much since the values of molecular weight remain
higher than when the first reaction moments happen similar. The performance of a prepolymerization
at mild conditions. This is due to the deactivation of step does not seem to affect the MWD, unlike the
the catalyst caused by the rapid increase of hydrogen concentration which has a strong effect in
the molecular weight.
 T40-100-4% T40-0-0%

T40-0-4%
T40-100-0%

2,5 3,5 4,5 5,5 6,5 7,5

log MW
Figure 8 – MWD for the polymers produced in experiments with different amounts of hydrogen.

When there is not hydrogen injected in the reactor, 485

there is no chain transfer agent, increasing the chain
length and so the molecular weight of the produced 465

BD (kg/m3)
polymer.
445
Bulk Density
425
The bulk density of the produced polymer in each
run can be analyzed in the next figures. Figure 9 405
shows the difference of bulk density with the type 0 25 50 75 100
of injection. % of alkane

300 Figure 10 - Variation of bulk density with the quantity of

alkane injected when a prepolymerization step is performed.
280
BD (kg/m3)

260 485
240 465
BD (kg/m3)

220
445
200
TDI
TDry-0-2% TDW
TDry-100-2% 425

405
Figure 9 - Variation of bulk density with the type of catalyst
injection. 0 25 50 75 100
% of alkane
It is worthwhile to note the difference of bulk
densities of polymers produced with different ways Figure 11 - Variation of bulk density with the quantity of
of injecting the catalyst. Polymers produced in a alkane injected without prepolymerization.
run with dry injection have a much lower density,
Analyzing the bulk density of the polymers, we can
which is expected since the particles formed are
conclude that there is slightly increase of bulk
hollow and flaky.
density with the increase of amount of alkane
In other hand, when the polymerization is introduced in the reactor, which can be attributed to
performed with the injection of alkane, the bulk the enhancement of local concentration on
density of the polymer obtained is a slightly higher, propylene inside the polymer. It is also very clear
once there is an enhancement of the local that the prepolymerization leads to higher bulk
concentration of propylene inside the particle. densities, which is explained by the higher surface
area of the polymer, making it better for propylene
Figures 10 and 11 show the variation of bulk insertion in the active sites of the catalyst. Figure
density with different amounts of alkane introduced 12 and 13 show the difference between each
in the reactor, with and without prepolymerization, concentration of hydrogen and how does it change
respectively. with the presence of alkane.
 485 60,0
50,0
465
BD (kg/m3)

Crystallinity (%)
40,0
445 30,0
20,0
425
10,0
405 0,0
0 1 2 4 TDI TDW
Conc. H2 (%) TDry-0-2% TDry-100-2%

Figure 14 - Variation of crystallinity with the type of catalyst

Figure 12 - Variation of bulk density with the concentration injection.
of hydrogen without alkane.
60,0
50,0
485
40,0

Crystallinity (%)
465 30,0
BD (kg/m3)

20,0
445
10,0
425 0,0

405
0 1 2 4
Conc. H2 (%)

Figure 15 - Variation of crystallinity with the quantity of

Figure 13 - Variation of bulk density with the concentration alkane injected without prepolymerization.
of hydrogen in the presence of alkane.
60,0
Regarding the hydrogen concentration, it is possible 50,0
Crystallinity (%)

to conclude that with alkane there is an increase in 40,0

density from 0 to 1% hydrogen, remaining constant 30,0
after 1%. Without alkane it is not possible to find a
relation between bulk density and hydrogen 20,0
concentration. 10,0
0,0
Differential Scanning Calorimetry

The crystallinity of the produced polymers in each

run can be analyzed in the next figures. Figure 14
shows the effect of alkane presence on the polymers
Figure 16 - Variation of crystallinity with the quantity of
produced when catalyst injection is made in dry alkane injected when a prepolymerization step is performed.
mode, Figure 15 and 16 represent the crystallinity
of samples produced with and without 60,0
prepolymerization with different amounts of iso- 50,0
hexane introduced. Figure 17 and 18 represent
40,0
Crystallinity (%)

how crystallinity is affected by the concentration of

hydrogen and its relation with amount of alkane. 30,0
The black bar represents the first heating curve and 20,0
the white one the second heating curve. 10,0
0,0

Figure 17 - Variation of crystallinity with the concentration

of hydrogen without alkane.
 60,0 step is performed, but not the molecular weight. By
the absorption of the reaction heat and also by
50,0
enhancement of the local concentration of
Crystallinity (%)

40,0 propylene inside the active sites of the catalyst, the

30,0 presence of an alkane leads to a higher activity
profiles. The presence of an alkane also affects the
20,0 bulk density in both cases (with and without
10,0 prepolymerization) but not the molecular weight
distribution.
0,0
Hydrogen concentration affects the instantaneous
rate of polymerization, the bulk density and the
molecular weight. A lower polymerization rate,
higher molecular weight and lower bulk density are
observed in the absence of hydrogen. It is observed
Figure 18 - Variation of crystallinity with the concentration
of hydrogen with alkane. also that the rate of polymerization is higher when
the catalyst is injected with mineral oil, having the
The crystallinity of the powder in all experiments produced polymer higher bulk densities.
was around 30% and after slow crystallization
[1] J. T. M. Pater, Study on the factors determining
process it raised up until between 45 and 50%.
powder morphology in catalytic propylene
Acknowledgements polymerization, 2001

I would like to thank to Dr. Timothy McKenna and [2] M. Monji, S. Abedi, S. Pourmahdian, F. A.
Professor Maria do Rosário Ribeiro for all the Taromi, J. Appl. Polym. Sci. 2009, 112, 1863–
patience and support. 1867.

A huge word of appreciation to Aarón J. Cancelas [3] Arash Alizadeh et all, Macromolecular
for all knowledge transmitted as well as for all the Symposia, Volume 333, Issue 1, pages 242–247,
kindness, willingness and sympathy during all the November 2013
internship.
[4] Hideharu Mori et all, Journal of Molecular
Conclusions Catalysis A: Chemical, Volume 145, Issues 1-2,
September 1999, 153-158
The instantaneous rate of polymerization increases
with the performance of a prepolymerization step, [5] J. P. B. Soares, T. F. L. McKenna, Polyolefin
thanks to a decrease of the local particle Reaction Engineering, Wiley-VCH, 2013
overheating in the initial instants of reaction. The
bulk density is higher when a prepolymerization