From the Shell Chemical Company Ltd.

, Carrington Plastics Laboratory, Carrington,

Manchester, England

Kinetics of the Polymerization of Ethylene with a Ziegler-

Natta Catalyst
I. Principal Kinetic Features

By M. N. BERGERand B. M. GRIEVESON

(Eingegangen am 1. Juni 1964)

SUMMARY:
The kinetics of the polymerization of ethylene was studied in an apparatus which is
described. A stable catalyst combination [Al(C,H,),Cl/y-TiCl,] which does not change
during the polymerization was used. Conditions are defined under which the reaction is (a)
independent of mass transfer rate (b) controlled by mass transfer. After an initial period,
the polymerization proceeds a t constant rate until the slurry is too thick to stir adequately.
The catalyst is neither occluded nor deactivated so that unlimited quantities of polymer
can be made from a given amount. When the reaction is not controlled by mass transfer,
the rate is linearly dependent on monomer and TiCI, concentration and is independent of
Al(C,H,),Cl. Hydrogen reduces the rate of the polymerization a t a constant partial pres-
sure of ethylene.

ZUSAMMENFASSUNG:
Die Kinetik der Athylenpolymerisation in einer speziellen Apparatur wurde untersucht.
Eine stabile Katalysator-Kombination (Al(C,H,)2Cl/y-TiCl,), die wahrend der Polymeri-
sation keine Anderung erfahrt, wurde angewendet. Es werden Bedingungen beschrieben,
unter denen die Reaktion (a) unabhangig, (b) abhangig von der Monomer-ubertragungs-
geschwindigkeit ist. Nach einer Anlaufperiode verlauft die Polymerisation mit konstanter
Geschwindigkeit, bis das Reaktionsgemisch nicht mehr ausreichend geriihrt werden kann.
Der Katalysator wird weder okkludiert noch desaktiviert, so da13 unbegrenzte Polymer-
mengen mit einer bestimmten Katalysatorkonzentration hergestellt werden konnen. So-
fern die Reaktion nicht durch den Monomer-Transport bestimmt wird, ist die Geschwin-
digkeit linear von Monomer- und TiC1,-Konzentration abhangig und unabhangig von der
Al(C,H,),Cl-Konzentration. Wasserstoff setzt bei konstantem Athylendruck die Polymeri-
sationsgeschwindigkeit herab.

Introduction

The studies published so far on the kinetics of the polymerization of

ethylene with heterogeneous ZIEGLER-NATTA catalysts have not yet pro-
gressed to the stage where a consistent picture emerges. Whereas exten-

80
 Kinetics of the Polymerization of Ethylene with a ZIEGLER-NATTA
Catalyst

sive studies on the polymerization kinetics of propylene 1-6) have produced

some satisfying quantitative informatioa and plausible mechanisms, the
information available on ethylene is comparatively difficult to evaluate
and to interpret. The ethylene case is, however, no less important than
that of propylene - both scientifically and industrially.

Scientifically, the interest lies firstly in the very much higher reactivity of ethylene com-
pared to propylene and other u-olefins. The propagation rate and the various transfer rates
might therefore be expected to stand in different relationships to each other than in the
case of propylene, etc. Secondly, the comparatively low solubility of ethylene in the hydro-
carbon solvents used in these polymerizations, coupled with its high reactivity might be
expected to lead to polymerizations which are controlled by rates of gas transfer rather than
by chemical factors. We believe that this 'point merits special attention, and we have at-
tempted in this paper to differentiate clearly between the conditions leading to ,,chemical
control" and those leading to mass transfer control. Dual kinetics of this type are very
much less likely to be met in the polymerization of propylene or other u-olefins, so that
ethylene is clearly differentiated in this sense.
Another point which we wish to emphasize concerns the choice of catalyst. Many of these
kinetic investigations in the literature both for ethylene as well as for the higher a-olefins
are based on catalyst combinations which undergo changes during p~lymerization'-'~).
Thus when a combination such as AIR,-TiC1, is used, the polymerization kinetics may be
complicated by a sequence of reactions such as:

AlR, + TiC14 -+ AlR,Cl + TiCl, + Re (1)

AlR,Cl + TiCl, + AlRCl, + TiCl, + Re (2 )

AIR, + TiCl, + AlR,Cl + TiCl, + Re (3)

which can proceed during p o l y m e r i z a t i ~ n ' ~ - ~Since

~ ) . the polymerizations depend on the
presence of TiCl, the overall kinetics and their interpretation can become very complicated.
Polymerization rates may he expected to rise or fall with time under such conditions, and
this is indeed often reported.
Thus the principal feature of the work of MESHKOVAet al.l0*l1)who polymerized ethyl-
ene with Al(C,H5),-Tic, and with Al(tC,H9),C1-TiCl, is that the rates rise to various
maxima from which they then descend continuously and, in some cases, quickly. The
shapes of the rate-time curves depend on the choice of the aluminium component, on cata-
lyst ratio, and on temperature. They depenil, in other words, on the kinetics of reactions
such as (1)-(3). Such reactions have been studied in isolation by a number of worker^'^-^').
Complications of this type can, however, be avoided by choosing combinations based on
TiCl, which are quite stable, and do not appear to change during polymerizations when
carried out at below 100°C. TiCl, is not reduced by AlR,C1 under these eondition~l~),
whereas AlR, can reduce the solid TiCl, further to TiCl,, a t least superficially. The use o€
AlR,Cl rather than AlR, might, therefore, be preferable for kinetic studies with TiC1,.
Nevertheless the extensive studies of the propylene polymerization by NATTAet al.1' led
to polymerization rates which were constant after an initial settling rate both with
A1(C,H5),Cl-TiCl, and with Al(C,H5),-TiCl,.

81
 M. N. BERCERand B. M. GRIEVESON

Comparatively little use has been made of such stable catalysts for the study of ethylene
polymerization. FUKUI 22) used the system Al(C,H,),-TiCI, in n-heptane which gave con-
stant rates of polymerization. The latter were directly proportional to [TiCI,] and to the
ethylene pressure. The rates rose markedly with AI(C,H,), concentration.
WILSONand HURLEY'~)used a three component system [Al(i-C,H,)C&-TiCl,-TiC14]
which they expected to be stable as regards valence change and in which the amount of cata-
lyst surface could be controlled. The ethylene polymerization rate nevertheless fell off quick-
ly unless the catalyst mixture was first aged. I n their experiments with Al(i-C4H9),-TiCI3
WILSONand HURLEYobserved similar declining polymerization rates which they ascribe
to the progressive coating of catalyst particles by polymer. Our own work as well as that
of F U K U does
I ~ ~not
) lend support to any catalyst occlusion theory.
Extensive studies of the ethylene polymerization with homogeneous (soluble) catalysts
have been reported 2''-zs), but such systems are mechanistically very different and are not
the subject of the present paper.
LIPMANand N O R R I S H have ~ ) recently described a very interesting study of the gas
phase polymerization of ethylene on a catalyst from Al(CH,),-TiCI,. The specific poly-
merization rate fell during each run due, apparently, to the progressive occlusion or de-
activation of catalyst in polymer. EDGECOMBE~), who also worked in the absence of solvent,
observed a similar effect.

I n view of the foregoing we have attempted to investigate the principal

features of the heterogeneous polymerization of ethylene by choosing as
simple a system as possible. This entails the following:

(a) The use of a stable catalyst system for which we have chosen
Al(C2H,)2C1- TiCl,.
(b) Defining conditions under which the polymerization rate is not con-
trolled by mass transfer processes, and applying these t o the study
of the principal kinetic features and t o determinacion of the rate
constants.

This paper deals with polymerization rates and how these vary with
certain parameters. A second paper deals with molecular weight relation-
ships and the individual rate constants for propagation and transfer.

Experimental Technique

Polymerization apparatus
Fig. 1 shows a general diagram of the polymerization apparatus together with the as-
sociated storage and purification equipment.
Before each polymerization the ethylene reservoir is charged from the storage cylinder.
The 3 1. reservoir which is thermostated a t 60 "C. holds up to 50 g. of ethylene a t 250 p.s.i.

82
 Kinetics of the Polymerization of Ethylene with a ZIEGLER-NATTA
Catalyst

VENT
VACUW
NITROGEN

<

Fig. 1. A. Manganous oxide column. B. Linde Sieve 4A column. C. Pressure relief vessels.
D. Solvent still; storage vessels for: E. High pressure ethylene. F. Ethylene. G. Solvent.
€ I.
Distilled solvent. J. AlEt,Cl. K. Tic& slurry. L. Hydrogen. M. Manometer. N. Relay
+ solenoid valve. P. Pressure gauges. Q. Pressure transducers. R. Oscillator - demodu-
lator. S. Strip-chart recorder. T. Thermostat baths. U. Polymerization reactor

The rate of ethylene consumption during a polymexization is followed by recording the

pressure change in the reservoir either visually (on pressure gauges) or automaticallyvia
the pressure transducerlstrip chart recorder system.
The ethylene reservoir is connected to the polymerization reactor uia a pressure reducing
valve, a solenoid valve, a gas purseation train, and a manometer. The manometer con-
tains adjustable contacts connected through a relay system to the solenoid valve so that
the required pressure can be set before a polymerization. As the ethylene polymerizes and
the reactor pressure falls, the manometer circuit opens the solenoid valve to admit more
ethylene from the reservoir until the reactor pressure is restored. The system enables us
to carry out polymerizations at constant pressure (* approx. 3 mm. Hg) in the range
50 to 800 mm. Hg.
The polymerizations were carried out in the 1 litre flanged reactor shown in Fig. 2.
The lower half of the pot is jacketed. The temperature in the reactor is controlled to i~
0.1 "C. by a rapid flow of water from a thermostat bath through the jacket. We normally
use only 200 ml. of polymerization solvent which allows rapid thermal equilibration with
the thermostatted jacket and also makes adequate stirring much easier.
The stirring of a heterogeneous polymerization system is extremely important. Pre-
liminary experiments showed that poor stirring resulted in low rates of reaction, but we

83
 M. N. BERCERand B. M. GRIEVESON

ALL LIQUID FEED

THERMOSTATTING LIQUID
IN

Fig. 2. Polymerization reactor

MAGNET

TO REACTOR
c,
Fig. 4. TiCl, storage vessel and sampling device
 Kinetics of the Polymerization of Ethylene with a ZIEGLER-NATTA
Catalyst

achieved very efficient stirring with a VIBROMIX stirrer. A perforated stainless steel disc
is vibrated vertically with a frequency of 50 sec-' and an amplitude of 2 mm. The profile
of the stirrer plate is designed to suck gas from the surface of the liquid and pump it vio-
lently downwards in a fine dispersion. The circulating streams of liquid and bubbles cause
vigorous agitation of the polymerization mixture. A stainless steel lid just above the liquid
surface prevents the reactants from being splashed on to the sides and roof of thereactor.
The VIBROMIX stirrer has the added advantage that it is very easy to obtain a vacuum
tight seal around the stirrer shaft.
Under normal polymerization conditions, the vibrating stirrer provides more than
sufficient agitation to keep the mixture saturated with monomer. The stirrer amplitude
may be reduced considerably before any marked fall of reaction rate can be observed
(Fig. 3). However, under conditions of high temperature or low monomer pressure, we have
observed reaction rates lower than would be expected.

73 MAXIMUM AMPLITUDE

Fig. 3. Effect of stirring rate on rate of polymerization; 200 ml. cyclohexane a t 40°C.;
760 mm. Hg; AlEt,Cl = 5 mmole/l.; y-TiC1, 0 = 1 mmole/l., A = 6 mmole/l.

Reagents
Nitrogen. The nitrogen supply had a water content of 5 to 10 ppm. and an oxygen con-
centration of approximately 10 ppm. This gas was further purified by passing through
manganous oxide and LINDEMolecular Sieve 4A.
Ethylene. Petrochemicals Ltd. polymerization grade ethylene from the storage cylinder
was passed through manganous oxide and Molecular Sieve 4 4 .just before entering the
polymerization reactor.
Solvent. Spectroscopic grade cyclohexane was sparged with pure nitrogen, then passed
through Molecular Sieve 4 A into a distillation flask, It was distilled against a stream of
nitrogen into a calibrated storage vessel immediately before use. The first 10% of the dis-
tillate was rejected.
DiethyIolurniniurn chloride. 99 yo Al(C,H,),Cl (Petrochemicals Ltd.) was distilled under
reduced nitrogen pressure. A small middle fraction boiling a t 67°C. a t 3.5 mm. Hg pres-
sure was collected in the alkyl storage flask.

85
 M. N. BERGERand B. M. GRIEVESON

Titanium trichloride. Purple y-TiC1, was prepared by reduction of freshly distilled

TiCl, with a 10% molar excess of Al(C,H5), in ,,SHELLSOL”solvent according to the
equation :
Al(C,H,), + 3TiC1, + AlCl, + 3TiC1, + 3C2H5* (1.)

The dark brown precipitate suspended in ,,SHELLSOL” was heated to 150°C. for 2 hrs. to
convert it to the purple y-form. The TiCl, precipitate which also contained AlCl, was
filtered off in a basket centrifuge, then washed several times with cyclohexane and re-
filtered. When the washings no longer showed any precipitate when treated with aqueous
ethanol, the TiCl, was slurried with cyclohexane to give a titanium concentration of about
200 mmole/l. The slurry was transferred to the storage vessel above the polymerization
reactor. Washing the TiCl, slurry made no apparent difference to its catalytic properties.
Similar polymerization results were obtained using unfiltered samples of the same batch
of TiC1,.
In order to transfer accurately known amounts of TiCI, from the storage vessel to the
reactor, we designed the sampling device shown in Fig. 4. The slurry was stirred rapidly
for a t least 5 min. before sampling. The pipette was lowered and the required volume of
slurry extracted. The pipette was then raised and turned until its tip extended over the
funnel. The contents of the pipette were then discharged into the funnel. While the TiCl,
sample was run into the reactor, fresh cyclohexane was sprayed on the inner walls of the
funnel to wash down any residual catalyst.
Hydrogen. Hydrogen (British Oxygen Co.) was purified by passing through a DEOXO
catalytic deoxygenator, then through a column of Molecular Sieve 4A. It was assumed
that the amount of hydrogen consumed in a polymerization is very small (one molecule
per polymer chain). The required volume of hydrogen was therefore admitted to the reac-
tor before the polymerization began. No further addition of hydrogen was made. The falling
pressure in the reactor due to polymerization was rektored by admitting ethylene only.

Polymerization technique

Immediately before a polymerization, the reactor and associated feed lines were evacu-
ated. After filling the system with nitrogen and evacuating again, the manometer contacts
were set to the required polymerization pressure, and ethylene was admitted. Al(C,H,),Cl
was added from the storage burette, followed by 150 ml. of cyclohexane. The stirrer was
started, and the TiCl, sample washed into the reactor. More solvent was added to give a
total of 200 ml. The ethylene pressure in the reservoir was noted when the TiCl, slurry was
admitted to the reactor, and readings of pressure and time were taken throughout the
polymerization.
A t the end of the polymerization the reactor was filled with nitrogen, then 50 ml ethanol
was added to the reactants. The decomposed polymer slurry was filtered when cold and
the polymer was allowed to stand with a cold mixture of ethanol and 10% concentrated
HCl for a t least 12 hrs. The polymer was filtered, washed thoroughly with acetone, then
dried a t 80 “C. There was no low molecular weight polymer dissolved in the polymerization
solvent.

86
 Kinetics of the Polymerization of Ethylene with a ZIEGLER-NATTA
Catalyst

REACTION TIME ( m i d

Fig. 5. Reproducibility of polymerization rate

200 ml. cyclohexane at 60°C.; y-TiC1, = 5.25 mmolell.; AlEt,Cl = 5.24 mmole/l. A Yield
of polymer in 2 hrs. = 17.1 g.; -t Yield of polymer in 2 hrs. = 16.5 g.; o Yield of polymer
in 2 hrs. = 17.3 g.

Experimental Results

1. The polymerization rate

Fig. 5 shows a typical record of t h e consumption of ethylene during

3 polymerizations carried out under identical conditions with t h e same
materials. It demonstrates the degree of reproducibility which can be
attained ( * 10 x). There are two prominent features in the curve:
(a) The initial polymerization rate is slightly higher t h a n t h e final rate
(7.2 l./hr. and 5.5 l./hr. respectively). I n almost every polymerization
which we have studied, the initial rate has been different from the final
rate. Sometimes t h e initial rate is higher t h a n t h e final rate, sometimes
lower. The duration of the initial period varies from 5 min. t o over 1 hr.
I n general t h e faster the final rate, the shorter is t h e initial period. We
have been unable t o correlate t h e initial rate or its duration with any of
the reaction variables. Changes in reaction rate a t the beginning of ZIEG-
LER-NATTA polymerizations have been observed b y other workers l ) .
(b) After the initial period all the polymerizations settle down t o a
constant reaction rate which can be maintained for many hours. Fig. 6
plots a polymerization a t low catalyst concentration which maintains a
constant rate for some 15 hrs. At this time the slurry contains 17 % of poly-

87
 M. N. BERGER
and B. M. GRIEVESON

REACTION TIME (hrs.)

Fig.6. Polymerization to high conversion

-
200 ml. cyclohexane at 40°C.; y-TiCl, = 0.525 mmole/l.; AlEt,Cl = 5.25 mmole/I.; Ethyl-
ene 643 mm. Hg. Arrow: 17% slurry; yield = 2020 g. polymerlg. TiCl,

Fig. 7. Microphotographs of a ZIEGLERPolymerization

Catalyst system: y-TiCl,/AIEt,Cl., room temperature. Magnification 700x. a) before
monomer addition; b) 2 hrs. reaction time; c) 5 hrs. reaction time; d) 70 hrs. reaction time

88
 Kinetics of the Polymerization of Ethylene with a ZIEGLER-NATTA
Catalyst

mer which is equivalent t o some 2,000 g. of polymer/g. TiC1,. When t h e

rate finally declines it does so because the reaction mixture is too thick t o
stir adequately.

2. Microscopic examination of the course of polymerization

We have attempted t o follow t h e course of a polymerization micro-

scopically. The reaction was carried out in a small stainless steel cell with
microscope cover-glasses sealed onto t h e top and bottom faces. The series
of photographs in Fig. 7 shows the changes taking place during a poly-
merization. Before polymerization starts, t h e catalyst consists of small
clusters of TiCl, particles. The individual particles are about 1 p in dia-
meter. During the polymerization, polymer seems t o precipitate around
the catalyst clusters. Comparison of t h e 2 and 5 hr. pictures with t h e
initial picture shows t h a t t h e site of the initial catalyst clusters can still
be identified, but each cluster grows more and more polymer until the
clusters merge.
Visual examination showed t h a t the outer surface of the clusters still
had the strong purple colour of the y-TiCI,. The impression was not t h a t
the catalyst particles became occluded in a layer of pure polymer, but
rather t h a t as the polymer grows i t enlrains catalyst. This seems t o indi-
cate t h a t t h e initial catalysL particles must break up duripg polymeri-
zation. The 1 p particles visible in the picture may not be whole crystals
of y-TiCl,, but loose aggregates of microcrystalline material which are
easily disrupted b y growing polymer. This process is more likely t h a n the
breaking of whole crystals.

3 . Polymerization temperature

Fig. 8 is a plot of the final steady polymerization rate a t different

temperatures. The rate increases as the temperature rises t o 50°C. and
falls off rapidly as t h e temperature rises further. Fig. 9 presents these
results as a n ARRHENIUSplot. Between 0" and 50 "C. the polymerization
obeys a linear relationship with a n apparent activation energy of 13.5
kcal./mole. Fig. 10 shows t h a t t h e solubility of ethylene in the polymeri-
zation solvent falls off rapidly as t h e temperature rises. There comes a
point when the rate of solution of ethylene in t h e solvent (which decreases
with t h e solubilicy) is too low t o satisfy the potential polymerization
activity of t h e catalyst. At this point (approx. 57 "C. under the conditions

89
 and B. M. GRIEVESON
M. N. BERGER

Fig. 8. Effect of temperature on polymerization rate

I
TiCl, = 5.25 mmole/l.; AlEt,Cl = 5.25 mmole/l.

-L
I
lo3
TEMPERATURE CKI
Fig. 9. ARRHENIUS plot of polymerization rates. ZIEGLER polymerization of ethylene
TiC1, = 5.25 mmole/l.; AlEt,Cl = 5.25 mkiole/l.; total pressure = 760 mm. H g
90
 Kinetics of the Polymerization of Ethylene with a ZIEGLER-NATTA
Catalyst

quoted) the ARRHENIUS relationship breaks down, and the reaction rate
actually falls with further increases of temperature.

TEMPERATURE PC.) . I
'0,

Fig. 10. Solubility and vapour pressure of ethylene in cyclohexane

Fig. 11. Effect of TiCI, concentration on polymerization rate

Temperature 30°C.; total pressure 760 mm. Hg; solvent volume 200 ml.; AIEt,Cl/TiCI,
molar ratio = 1

91
 M. N. BERGERand B. M. GRIEVESON

4. Catalyst concentration
Under ideal conditions the polymerization rate is directly proportional
t o the TiCl, concentration as shown in Fig. 11. As suggested above it is
possible to carry out polymerizations under conditions where the rate of
polymerization is no longer governed by chemical factors. This occurs
when the reactivity of the catalyst is high and the rate of transport of
monomer is low. The latter might then become rate determining, so that

ITiCIJl(mmole/l.)

Fig. 12. Effect of catalyst concentration under conditions of “diffusion control”

Temperature 60 “C. ; total pressure 760 mm. Hg; solvent volume 200 ml.; AlEt,CI varied

-5 6
L’
7

-
Y
5 5
z
g4
4
V

: 3

21 10 20 30 40 50
0
[AlEt,CI] (mmole/l.)
Fig. 13. Effect of [AlEt,Cl] on polymerization rate
Total pressure 760 mm. Hg; [TiCl,] = 5.25 mmole/l.; x = 60°C.; o = 30°C.

92
 Kinetics of the Polymerization of Ethylene with a ZIEGLER-NATTA
Catalyst

the response to increasing catalyst concentration is reduced. Thus Fig. 12

shows that at 60 "C. the rate has become roughly independent of catalyst
concentration. Under these conditions the reactivity and monomer trans-
fer rate are such that them latter mainly influences the polymerization rate
in the range of ca:alyst concentration studied.

Temperature 4OoC.; TiCl, = 5 mmole/l.; total pressure 760 mm. Hg

ETHYLENE PARTIAL PRESSURE (mm.Hg 1

Fig. 15. Effect of monomer concentration on polymerization rate

TiCl, = 5.25 mmolell.; AlEt,Cl = 5.25 mmole/l.; o = 30°C.; A = 40°C.; 0 - 60°C.
93
 M. N. BERGERand B. M. GRIEVESON

Where the rate does vary directly with catalyst concentration it does
so according t o a first order relationship with [TiCl,] and a zero order
relationship with [Al(C,H,),Cl]. Fig. 13 and 14 show that the rate is
independent of [A.l(C,H,),Cl] where this is above 1 mmole/l. Below this
level, the rate falls quickly with [Al(C,H,),Cl]. We 'kannot be certain
whether this is due to the partial destruction of the small amounts of
aluminium alkyl by impurities, or whether the catalyst really requires
a minimum of alkyl in this concentration range.
8

5. Monorrier concentration
Fig. 15 is a log-log plot of polymerization rate a t various temperatures
against partial pressure of ethylene. The straight lines show that
Rate - apn

where p is the partial pressure and n is the order of the reaction. The
plots correspond t o the following values of n:

Temp. ("C.) . . .. . 30 40 60
n ............. 1.1 1.0 2.2

We thus have a first order dependence a t 30 "C. and 40 "C. and roughly
a second order dependence a t 60°C. where the rate is mass transfer
controlled. I n the absence of more results, we do not a t this stage attach
any theoretical significance t o the second order dependence.

6 . The effect of hydrogen

Hydrogen is a well established transfer agent in ZIEGLER-NATTA poly-
merizations and its quantitative effect on molecular weight is t o be de-
scribed in a later paper. Hydrogen reduces the rate of the ethylene poly-
merization quite apart from its effect on feed gas composition. The reduc-
tion in the rate due t o hydrogen is best demonstrated by plotting the
specific reaction rate (rate a t unit ethylene pressure) against the partial
pressure of hydrogen (Fig. 16).

Discussion
1. Course of the reaction
The constant polymerization rate t o high conversion is well established
in our experiments, but is in conflict with a number of published obser-

94
 Kinetics of the Polymerization of Ethylene with a ZIEGLER-NATTA
Catalyst

PARTIAL PRESSURE OFHYDROGEN ( m d

Fig. 16. Effect of hydrogen on rate

Temperature = 40°C.; total pressure = 760 mm. Hg. y-TiC1, = 5.25 mmolell.; AlEt,Cl =
5.25 mmolell.

vations. It does not agree with any theories of catalyst occlusion13) or

deactivation14) which have been invoked by a number of workers t o ex-
plain their declining polymerization rates.
Our findings are t h a t a typical ZIEGLER-NATTA
catalyst can be expected
t o give a constant rate of polymerization of ethylene which can be main-
tained to very high conversions and high slurry concentrations. The
catalyst is neither occluded nor deactivated. The number of active sites
remains constant. Contrary findings may be due to:
(a) The use of an inherently unstable catalyst combination.
(b) The progressive introduction of impurities.
(c) Inadequate agitation leading to progressively slower transfer of mono-
mer as the slurry thickens.

The case established here for ethylene is in agreement with NATTA and
PASQUON’S findings for propylenel) which after an initial settling period
polymerizes a t a constant rate to high conversion. These authors observed
settling periods during which the rates are continuously changing - either
rising or falling. Our experiments give initial rates which are themselves
constant until they suddenly change t o the final rates. The latter are
reproducible and predictable whereas the initial rates are not. We are
inclined t o adopt NATTA and PASQUON’S picture of changes in the effective
surface area of the catalyst during the settling period. We cannot, how-
ever, account for the fact that the initial rate is not reproducible when
the same batch of TiCl, is used for various runs.

95
 M. N. BERGER
and B. M. GRIEVESON

2 . Kinetics and mechanism

The principal reaction steps which have been proposed for the poly-
merization of ethylene and cr-olefins are as follows1):

(a) Cat.-CH2CH,. . . . . .CH,

CH, - CH$ Cat.-CH,CH,CH,CH, ......CH,
k,

CH, = CH,
(b) Cat.-CH,CH,. .....CH, + Cat.-CH,CH3 + CH, = CH.. ... .CH,
kM

(c) Cat.-CH,CH,. .....CH, + Cat.-H + CH, = CH.. ... .CH,

k,

and in the presence of hydrogen

(d) Cat.-CH,CH,. .....CH, H, -.+ Cat.-H + CH,CH,. .... .CH,

kH

"Cat" represents the complex active centres on the TiCl, surface which
have been postulated. NATTAand PASQUON~) found that the rate of poly-
merization of propylene, which is equal to the rate of the propagation
reaction, is directly proportional both to [TiCl,] and [monomer], whilst
i t is independent of [All when this is above a certain value:

Rate = k [TiCl,]'[ C,H,]'[Al]"

The results which we present here for ethylene are identical so long as
the reaction is under "chemical control". This refers to reaction temper-
atures below 50 "C., moderate catalyst concentration and good agitation.
The relationship shows that the number of active centres and their re-
activity in propagation is independent of [Al(C,H,),Cl]. Similarly the
ratio Al/Ti does not affect the rate. This is in contrast t o the results of
FUKUI,,) who found t h a t the ethylene polymerization rate a t a given[TiCl,),
rose with [Al(C,H,),]. This may be due to a reaction such as (3), which will
not take place with AlEt,Cl under our conditions. I n contrast to FUKUI,
NATTAand PASQUON~) did not observe this effect with Al(C,H5), in the
polymerization of propylene. This might mean that increasing concen-
trations of AI(C,H,), produce progressively more active sites on a given
amount of TiC1, surface which initiate the polymerization of ethylene but

96
 Kinetics of the Polymerization of Ethylene with a ZIEGLER-~LATTACatalyst

not t h a t of propylene. These sites, based on t h e Ti's reduction state might

be electronically unsuitable for the propylene polymerization, or they might
be unable t o accommodate the propylene molecules for steric reasons
which do not apply t o ethylene.
The overall apparent activation energy for t h e polymerization is
13.5 kcal./mole. Fig. 10 gives the measured solubility of ethylene in cyclo-
hexane a t various temperatures. From this we can calculate t h e activation
energy corrected for constant monomer concentration in solution. This
gives a value of 17.3 kcal./mole.
We may thus write a general rate for the polymerization of ethylene
from the results present above, which applies t o t h e non-mass transfer
controlled reaction :
-17300
Rate (in mole/l. hl.) = A - [TiCl,][ethylene] . e RT where A = 6.1 * 1015
l./mole hr. and [ethylene] is t h e actual concentration in the solvent in
mole/l. The TiCl, concentration is expressed as mole/l. and refers t o the
samples used in our work. The constant A may vary with t h e size and
shape of t h e catalyst particles if (as is likely) the reaction rate depends
on t h e surface area of the catalyst as well as t h e weight.
The apparent activation energies reported in t h e literature for ZIEGLER-
type polymerizations of ethylene vary from approximately 1 t o 12 kcal./
m01e9,12,22,24,29). The catalyst system nearest t o t h a t used in this work
is t h a t of F U K U IA1(C2H5),/TiCl,
~~) who obtained a n overall activation
energy of 1.6 kcal./mole and a corrected value of 7.8 kcal./mole. These
values are substantially lowe1 t h a n ours.
Most workers who have studied t h e effect of monomer concentration
on t h e rate of polymerization of a-olefins report a first order dependence
such as we find under non-diffusion controlled conditions. Second order
kinetics, such as we find a t the higher temperatures, have also been
reported 30).

Conclusions

We conclude from the results givenin this paper t h a t the complexity

of the kinetics of t h e ethylene polymerization as presented in much of
theliterature can be avoided. By choosing a stable catalyst and b y working
under conditions of true chemical control and high purity, one can expose
the really fundamental features of t h e polymerization. They include :

97
 M. N. BERGERand B. M. GRIEVESON

(a) A catalyst of infinite life which becomes neither occluded nor de-
activated.
(b) Polymerization rates which are directly proportional to [TiCl,] and
[ethylene] but independent of [AlEt,Cl].
(c) An apparent overall activation energy of 13.5 kcal./mole, and a cor-
rected value of 17.3 kcal./mole.
.(d) A tendency for the polymerization to become controlled by mass
transfer of ethylene.

The authors express their thanks to Dr. R. N. HAWARDfor many

valuable discussions and suggestions, and to Mr. D. WORRALL for his
assistance with the experimental work. They also wish to express their
thanks to the Directors of SHELLChemical Company Ltd. for permission
to publish this work.

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99