Note: Descriptions are shown in the official language in which they were submitted.
`
- 1 - 31124
ETHYLENE POLYMERISATION PROCESS
The present invention relates to a process for the
production o a polymer or copolymer of ethylene.
~ ccordin~ to the present invention there i9 provided
a process for the production o an ethylene polymer which
proaess comprises contacting ethylene, or a mixture of
ethylene and a monomer which is copolymerisable with
ethylene, under polymerisation conditions with a catalyst
system obtained by mixing together 1) an organic compound
of a metal of Group IIA of the Periodic Table or of
aluminium, or a complex of an organic compound of a metal
of Group I~ or Group IIA of the Periodic Table with an
organic compound of aluminium; and 2) the reaction product
obtained by reacting together reagents consisting of a
component I which is at least one substantially inert
solid particulate material having reactive sites (as
hereinafter defined), a component II which is an organic
magnesium compound or a complex or mixture of an organic
magnesium compound and an aluminium compound, a component
III which is at least one halogen-containing compound
selected from hydrogen halides, boron halides, halogens,
inter-halogen compounds and halides of elements of Groups
IVB, VB and VIB of the Periodic Table, and a component IV
which is titanium tetrachloride.
For convenience, the substantially inert solid
particulate material having reactive sites will be
referred to hereafter as the solid particulate materialO
The formulae A to G in the attached drawing represent
comp~unds which may be used in the present invention~
All references herein to the Periodic Table are to
the Short Periodic rable as set out inside the back cover
of "General and Inorganic Chemistry" by J R Partington,
Second Edition, published by MacMillan and Company
Limited, London in 1954.
~4~9~
- 2 - 31124
The process of the present invention is preferably
used to effect the copolymerisation o ethylene with
another monomer. The other monomer i9 preferably an
alpha~olein monomer o the formula A in which,
Rl is an alkyl radical.
In the ~ormula A, it is preferred that the group
contains not more than 10 carbon atoms and conveniently
contains up to 4 carbon atoms. Thus, the monomer of
formula A may be propylene, butene-l, pentene-l or
hexene-l or 4-methylpentene-1 or any other monomer which
satis~iès formula A.
If the process of the present inventîon is used for
the copolymerisation of eth~lene, the quantity o the
comonomer which is copolymerised with the ethylene is
conveniently in an amount such that the polymer formed has
a density in the range of 915 up to 940 kg/m3. The
molar ratio of ethylene to the comonomer during the
polymerisation is typically in the range from 15:1 to
1:1, but it will be appreciated that the optimum ratio
will be dependent on the particular comonomer being used.
`~ The polymerisation process can be effected under any
conditions of temperature and pressure which have
previously been used for the polymerisation and
copolymerisation o ethylene. Thus, the temperature may
be in the range from 2QC up to 300C and the pressure may
be from below 1 kg/c~2 up to 3000 kg/cm2. However, it
is pre~erred that the polymerisation is carried out under
relatively moderate conditions of temperature and
pres~ure. Thus, it is preferred that the temperature is
in the range from 50C up to 100~ and that the pressure
is from 2 kg/cm2 up to 50 kg/cm2. Especially
preferred polymerisation conditions are at a temperature
in the range from 70 up to 95C and at a pressure of from
1 5 kg/cm2 up to 30 kg/cm2.
Component 1) of the catalyst may be an organic
magnesium compound of the same type as is used as
~4~
- 3 - 31124
component 2) in the production of the titanium~containing
material. If the magnesium compound is a Grignard reagent
it~is preferred that it is substantially ether-free.
~l~ernatively, component 1) may be a complex o a metal of
Group I~ of the Periodic Table with an organic aluminium
compound such as a compound of the type lithium aluminium
tetraalkyl. Useful materials for use as component 1) o
the catalyst are organic aluminium compounds such as
aluminium hydrocarbyl halides, aluminium hydrocar~yl
sulphates, aluminium hydrocarbyl hydrocarbyloxy compounds
and in particular, aluminium trihydrocarbyls or
dihydrocarbyl aluminium hydrides. The aluminium
trihydrocarbyl is ~referably an aluminium trialkyl in
particular one in which the alkyl group contains from 2 up
to 10 carbon atoms, for example aluminium triethyl,
aluminium tributyl, or aluminium trioctyl.
Component 2) of the~ catalyst system is a transition
metal composition. This is obtained by reacting together
four different components. The xeaction product may be
obtained by mixing these four components together in a
single stage but it is preferred to produce the reaction
product by reacting the various components in more than
one stage~ It is particularly preferred to contact the at
least one solid particulate material which is component I
with one of components II, III or IV, and then treat in
turn with the other two components. The treatments with
components II, III and IV may be effected by adding each
component, in turn, to the reaction mixture rom the
previous stage, and this procedure may be effected without
separating the reaction product from the reaction mixture
of one stage before adding a further component to effect
the next stage However, a solid reaction product may be
! separated from the reaction mixture at the end of any, or
all, of the treatment stages and the separated solid
reaction product is then preferably washed. If an excess
~14~
- 4 - 31124
of any of components II, III or IV is used, it is very
desirable to separate and wash the solid reaction product
at the end of any stage in which such an excess is used.
It i9 pre~erred, but not essent~al, to separate and wash
the solid reaction product on completion of the ~irst
treatment stage and al 30 on completion of the treatment
stage in which the halogen-containing compound is used.
It is generally preferred that the treatment with titanium
tetrachloride is effected as the last stage and in this
preferred process the at least one solid particulate
material is treated first with component II or
component III, the reaction product is treated with
whichever of component II or component III was not used in
the first stage and then finally with the titanium
tetrachloride. It may, however, be desired to effect an
intermediate treatment with titanium tetrachloride in
addition to a final titanium tetrachloride treatment. Any
intermediate treatment with titanium tetrachloride is
conveniently effected after the irst treatment stage in
which component I is reacted with component II or
component III and before the su~sequent stage in which the
solid reaction product is treated with the other one of
component II or component III.
Component I which is used in the production of
catalyst componant 2) is at least one substantlally inert
solid particulate material having reactive sites (as
hereinafter defined). By "reactive sites" are meant those
sites which are capable of abstracting a magnesium
hydrocarbyl compound from a solution thereof. The number
of reactive sites can be determined by adding, to a known
weight of the at least one solid particulate material, a
solution containing an excess quantity of a magnesium
hydrocarbyl compound, stirring the mixture at ambient
temperature for an hour and analysing the supernatant
liquid to determine the quantity of the magnesium
~ 5 - 31124
hydrocarbyl compound which remains in the solution, from
which can be calculated the number o moles of magnesium
hydrocarbyl compound which have been abstracted ~xom the
solution for each gramme of the solid particulate
S material, this being e~uivalent to the proportion, in
moles, of the reactive sltes.
The solid particulate material which is used as
component I in producing th~ transition metal composition
which is component 2) of the catalyst system, may be any
such material which has been proposed previously for use
in an olefin polymerisation catalys~ system. Thus, the
solid particulate material may be an organic or inorganic
compound of a metal, which term is used herein to include
silicon, such as a metal halide, or a metal oxide or
mixtures or reaction products of two or more such metal
compounds.
It is particularly preferred that the solid
particulate material which is component I is a metal
oxide, and in particular is an oxide of a metal of Groups
I to IV of the Periodic Table. Solid oxides which may be
used as component I include those with a substantially
inert matrix material wherein at least some of the
reactive sites are present in a hydroxylic surface (as
hereinafter defined) which is free from adsorbed water.
By "hydroxylic surface" is meant a surface having a
plurality of -OH groups attached to the surface, the
hydrogen atom of the -OH group being capable of acting as
a proton source, that is, having an acidic function. A
matrix material having a hydroxylic surface is
substantially inert in that the bulk of the matrix
material is chemically inert.
The at least one solid particulate material may be
silica, alumina, magnesia, mixtures of two or more
thereof, for example magnesium tri~ilicate which may be
represented as (MgO)2(SiO2)3xH~O (x is a positive
~; .
- 6 - 31124
number), thereon and containing minor amounts, for example
less than lO~ by weight, o other suitable solid
particulate materials ~uch as zinc oxide. Particularly
u3eul solid particulate materials include alumina and
silica.
The at least one solid particulate material
preerably has a surace area of at least 30 m2/g,
particularly a~ least 100 m2/g, and especially at least
200 m2/g~ Useul forms of the at least one solid
particulate material may be obtained by heating an
inorganic oxide or hydroxide in an inert atmosphere,
and/or at a reduced pressure, to a temperature of at least
200C and not more than l200C and preerably in the range
300C to 1000C. A suitable inert atmosphere for heating
is nitrogen and a suitable reduced pressure is less than
10 mm of mercury. The temperature used will be dependent
on the material being heated. Thus, if silica is being
heated, it i~ especially pr~ferred to use a temperature in
the range 320C up to 400C, for example 350C. Using
hydrated alumina, for example Boehmite (which may be
regarded a~ hydrated gamma-alumina), or aluminium
hydroxide~ it is especially preferred to use a temperature
in the range 400C up to 1000C, for example 500C.
Alternatively, the at least one solid particulate material
may be heated in a high boiling point inert hydrocarbon,
or halohydrocarbon, liquid, for example under azeotropic
conditions. Heating in the presence o an inert liquid
medium is typically effected at a temperature in the range
100C up to 200C using a liquid having a boiling point in
this range.
Component II of the reaction mixture which i~ used
to produce the transition metal component of the catalyst
is an organic magnesium compound or complex or mixture
thereof with an aluminium compound. The organic magnPsium
compound is a compound of formula B in the attached
7 ~ 31124
formula drawings, the complex thereof with an aluminium
compound is repre~ented by ~ormula C in the attached
formula drawings and the mixture thereof with an aluminium
compound is represented by the ormula D in the attached
~ormula drawings.
In the formulae B, C and D,
each R , which may be the same or different, is a
hydrocarbon radical;
each X, which may be the same or different, i5 an
oxyhydrocarbon radical or a halogen atom other than
fluorine:
a has a value of greater than 0 up to 2;
b has a value of greater than 0 up to 2; and
c has a value of from 0 up to 3.
The groups R are all typically alkyl groups and
conveniently are alkyl groups containing from 1 up to 20
carbon atom~ and especially 1 up to 6 carbon atoms. The
groups X are all preferably halogen atoms, other than
fluorine, for example chlorine or bromine atoms. The
value of a is preferably at least 0.5 and it is
particularly preferred -that the value of a is 2~ The
value of b is typically in the range O.OS up to 1Ø The
value of c is typically at least 1 and is preferahly 3.
The organîc magnesium compound of formula B, which is
also present in the materials of formulae C and D, may be
a Grignard reagent such as ethyl magnesium chloride or
butyl magnesium bromide or may be a compound such as ethyl
magnesium ethoxide, but is preferably a magnesium
dihydrocarbyl compound such as diethyl magnesium or
dibutyl magnesium. Whilst the aluminium compound, which
is present in the materials of formulae C and D, may be
aluminium chloride or aluminium bromide, it is preferably
an organic aluminium compound such as ethyl aluminium
dichloride, diethyl aluminium monochloride or diethyl
aluminium ethoxide, and is particularly a compound such as
aluminium triethyl or aluminium tributyl.
- 8 - 31124
It will be appreciated that the materials of formulae
C and D ma~ be present together as an equilibrium mixture
and indeed such a mixture may be obtained merely by mixing
together the organ.ic magnesium compound with the aluminium
compound when the resultant product may be a m~xture of
the organic ma~nesium compound, the aluminium compound and
the complex of formula D. It will be appreciated that it
is preferred that the compound of formula B, C or D is a
material which i3 soluble in inext liquid hydrocarbons.
m e organic magnesium compound, or the complex or
mixture thereof with the aluminium compound, is
conveniently added aq a liquid medium to a solid material
which is either the at least one solid particulate
material or the product of reacting the at least one solid
particulate material with one or both of components III
and IV. The solid material to which component II is
added, may be suspended in an inert liquid such as an
aliphatic hydrocarbon. The liquid medium containing
component II is conveniently a solution of the organic
magnesium compound, or the mixture or complex thereof with
the aluminium compound, in an inert liquid such as a
hydrocarbon liquid, for example hexane, heptane, octane,
decane, dodecane or mixtures of the isomers thereof, or
inert halohydrocarbons such as chlorobenzene.
The quantity of the compound B, C or D which is added
; to the at least one solid particulate material, or the
product of reacting the at least one ~olid particulate
material with one or both of components III or IV, is
dependent on the nature of the at least one solid
particulate material, the surface area thereof and in
particular any heat treatment used in obtaining the solid
; particulate material. The quantity of the compound B, C
or D which is added may be in excess of that required to
saturate the surface of the at least one solid particulate
material, ~hat is in excess of one mole for each mole of
.
- 9 - 31124
the reactive sites present on the at least one solid
particulate material. When the solld particulate material
is a metal oxide, typically at least some of the reactive
sites are sur~ace hydroxyl groups.
The quantity of the compound B, C or D which is used
is also dependent on the quantity of the halogen-
containing compound which is component III and, in
particular, it is preferred that the molar quantity of the
compound B, C or D which is used is less than the amount
of the halogen-containing compound which is component III
and in particular is from 0.25 up to 0.8 mole of compound
B, C or D for each mole of the halogen-containing compound
which i~ component III.
The compound B, C or D can be added to the at least
one solid particulate material, or the prodùct of the at
least one solid particulate material and one or both o
components III and IV at any suitable temperature, for
example from O~C up to 100C, conveniently at ambient
temperature, that is from about 15C up to about 25C.
After adding the compound B, C or D to the at least one
solid particulate material, or the product of the at least
one solid particulate material and at least one of
components III and IV, reaction is conveniently effected
by allowing the materials to remain in contact for at
least 5 minutes and not more than 20 hours, for example
0.25 up to 6 hours. After the desired period of
contacting, the solid material which is the reaction
product may be separated from the liquid medium, for
example by filtration, decantation or evaporation, and
may then be washed one or more times. If desired, the
solid material whic~ is the reaction product may be
~ubjected finally to an optional low pressure (about 1 mm
of mercury) treatment at ambient tempsrature, or higher,
for a time of up to several hours, for example 2 hours
before being used in the next stage of the preparation.
~ 10 - 31124
However, these separation and wa~hing operations are not
essential, particularly if component II is used in an
amount of less than one mole for each mole o reactive
sites present in the at leaqt one solid particulate
material.
The at least one halogen-containing compound which is
component III i9 preerably a chlorine-containing
compound. If the halogen~containing compound is a halide
of an element of Groups IVB, VB or VIB of the Periodic
Table, it is preerred that this is an element of the
second or third series. The at least one halogen-
containing compound may be a hydrogen halide, a silicon
halide o~ the formula E, a carhoxylic acid halide of the
formula F, a hydrocarbyl halide of the formula G, a
phosphorus halide, a phosphorus oxyhalide, a boron halide,
sulphuryl chloride, phosgene, nitro~yl chloride, chlori~e,
bromine, a chlorinated polysiloxane or an ammonium
hexafluorosilicate, wherein
R3 is a hydrogen atom or a hydrocarbon radical;
R4 is a hydrocarbon radical;
R5 is the residue obtained obtained by removing one
or more hydrogen atoms from a hydrocarbon compound;
Z i9 a halogen atom other than fluorine;
d is 0 or an integer from 1 up to 3; and
e is an integer from 1 up to 10.
In the silicon halides of formula E, it is preferred
that R3 i~ an alkyl group containing one up to six
carbon atoms or an aryl, alkaryl or aralkyl group
containing 6 up to 15 carbon atoms. In the carboxylic
acids of formula F, it is preferred that R4 is an alkyl
group containing 1 up to 4 carbon atoms or an aryl,
alXaryl or aralkyl group containing 6 up to 12 carbon
atoms. In the hydrocarbyl halides of formula G, the group
R may be a carbon residue or may include hydrogen
atoms and Z, or each Z, is preferably attached to an
aliphatic carbon a~om.
~ 31124
The silicon halides of formula E include silicon
tetrachloride, silicon tetrabromide and halosilanes such
as trichlorosilane, diethyl silicon dichloride, monobutyl
silicon trichloride and monoethyl silicon trichloride.
The carboxylic acid halides o~ ormula F include
acetyl chloride, benzoyl chloride and p-methylbenzoyl
chloride.
The hydrocarbyl halides of formula G include carbon
tetrachloride, chloroorm and l,1,1-trichloroethane.
~uitable materials for use as the halogen-containing
compound are halogenating agents by which is meant a
halogen-containing compound which, when reacted with the
at least one solid particulate material, or the product o~
reacting the at least one solid paxticulate material with
a~ least one of the other components, gives a solid
reaction product having an increased halogen content.
The at least one halogen-containing compound is
conveniently added in a liquid form to a solid material
which is the at least one solid par~iculate material, or
the solid reaction product from a previous treatment
stage. This addition may be effected by using a solution
of the halogen-containing compound in an inert solvent
such as an aliphatic hydrocarbon solvent. Thus, the
reaction with the solid material is conveniently carried
out by suspending the solid material in a liquid medium
which is, or which contains, the halogen-containing
compound. However, the halogen-containing compound may be
used in the gas phase. Using a halogen-containing
compound which is gaseous at ambient temperature, for
example hydrogen chloride or boron trichloride, the gas
is conveniently passed into a stirred suRpension
containing the solid material. Alternatively, a gaseous
halogen-containing compound may be passed, optionally as a
mixture with an inert gaseous diluent such as nitrogen,
through a bed of the solid material, conveniently a
- 1~ - 311~4
1uidised bed. This latter technique can be used both
with halogen-aontaining compounds which are gaseous at
ambient temperature and also with halogen-co~taining
compounds having boiling temperature~ above ambient
temperature.
The reaction with the at least one halogen-containing
compound can be effected at ambient temperature, or at an
elevated temperature which may be as high as 600C but
typically does not exceed 100C. The preferred
temperature will be dependent on the particular halogen-
containing compound, for example, using silicon
tetrachloride the temperature is preferably at least
60C.
The quantity of the at least one halogen-containing
compound is preerably ~ufficient to provide at least one
halogen atom at every reactive site on the solid
particulate material. It is convenient to add the
halogen-containing compound in the amount of 1 mole for
every mole of reactive sites on the solid particulate
material. However, it should be appreciated that smaller
quantities of the halogen-containing compound may be used,
for example as little as 0.2 mole of the halog0n-
containing compound for each reactive site.
Alternatively, an excess of the halogen-containing
compound may be used, and this is conveniently achieved by
suspending the solid material in an excess quantity of a
liquid halogen-containing compound. The reaction with the
at least one halogen-containing compound is conveniently
effected for a time o from 0.25 up to 10 hours,
preferably from 1 up to 5 hours.
After the reaction with the at least one halogen-
containing compound, the reaction product is conveniently,
but not necessarily, separa~ed from the reaction medium
and washed several times.
j ~ ,
~ 13 - 31124
It is preferred to add the titanium tetrachloride
which i5 component IV to a product obtained by reacting
the at least one solid particulate material, either
simultaneously or in succession, with component II and
component III. The reaction may be effected by adding a
solution of titanium tetrachloride to a solid material
which is the reaction product obtained from the preceding
stages. Alternatively, this solid material may be
suspended in undiluted titanium tetrachloride. When
undiluted titanium tetrachloride is used, the amount
thereo will be such as to provide more than one mole of
titanium tetrachloride for each mole of the reactive sites
preRent on the at least one solid particulate material.
If a solution of the titanium tetrachloride is used, the
amount of titanium tetrachloride which is added may be
less than one mole for each mole of reactive sites, and is
typically in the range from 0.1 mole up to 0.8 mole of
titanium tetrachloride for each mole of reactive sites.
The amount of titanium tetrachloride is especially in the
range 0.15 up to 0.6 mole of titanium tetrachloride for
each mole of reactive sites on the solid particulate
material .
The reaction of the titanium tetrachloride with the
solid material is conveniently carried out at a
temperature of from 0C up to the boiling temperature of
titanium tetrachloride which i~ about 137C at atmospheric
pressure. If the solid material i~ contacted with neat
titanium tetrachloride this may be carried out at the
boiling temperature of titanium tetrachloride. However,
if the solid material is contacted with a solution of
titanium tetrachloride this may conveniently be effected
by stirring the mixture at ambient temperature. After
adding the titanium tetrachloride to the solid material,
the materials are conveniently allowed to remain in
contact for from 0.25 up to 10 hours, preferably 1 up to 5
- 14 - 31124
hours. After the desired period of contacting, the solid
product obtained may be sepaxated rom the li~uid reaction
medium and wa#hed several times with an inert liquid
medium, but this ~eparation and washing is not essential.
If the treatment with titanium tetrachloride is
efected as an intermediate stage in the process, this
intermediate stage is conveniently effected using an
excess quantity of titanium tetrachloride. EIowever, it is
preferred that there is, in addition to an intermediate
treatment with titanium tetrachloride, a final treatment as
hereinbefore described. Alternatively, there may be two
final treatments with titanium tetrachloride, the irst
being with a minor proportion ~less than 1 mole of
titanium tetrachloride for each mole of reactive sites),
and the second being with an excess quantity of titanium
tetrachloride, conveniently using undiluted liquid
titanium tetrachloride.
It will be appreciated that the reaction product
which is component 2) of the catalyst contains a titanium
halide and a magnesium halide composition supported on a
solid particulate material.
The proportions of components 1) and 2) of the
catalyst system may be varied within a wide range as is
well known to the skilled worker. The particular
preferred proportions will be dependent on the type of
materials used and the absolute concentrations of each
material, but in general we prefer that for each gramme
atom of titanium which is present in component 2) of the
catalyst system, there is present at least one mole of
component 1), and preferably at least 5 moles of component
1) for each gramme atom of titanium. The number of moles
of component 1) for each gramme atom of titanium which is
present in component 2) may be as high as 1000 but
conveniently does not exceed S00.
~410~
- 15 - 31124
When the process of the present invention is be~ing
used to effect the copolymerisation of ethylene, it is
preferred to carry out the copolymerisation using a
mixture of ethylene and the de~ired comonomer, for example
butene-l or hexene-l, wherein the mixture o monomers has
essentially the same composition throughout the
polymerisation process.
The process of the present invention can be used for
the polymerisation or copolymerisation of ethylene to give
a high yield of polymer. Since catalysts of the type
used in th~ process of the present invention are
susceptible to the presence of impurities in the
polymerisation system, it is desirable to effect the
polymerisation using a monomer, and a diluent if this is
being used, which has a high degree of purity. Thus, it
is preferred that the monomer contains less than 5 ppm by
weight of water and le~s than 1 ppm by weight of oxyaen.
Materials having the desired high degree of purity can be
obtained in the manner known in the art, for example by
passing the material to be purified through a bed of a
molecular sieve material and also through a bed of
material which will remove o~ygen containing impurities.
The ethylene polymerisation process is conveniently
effected in the substantial absence of any liquid medium
and such a process is particulArly effected using a
fluidised bed reactor system. In such a fluidised bed
reactor system, the 1uidising gas is conveniently the gas
mixture to be polymerised together with any hydrogen which
is present as a chain transfer agent to control molecular
weight. Thus, for the copolymerisation of ethylene and
butene-l to produc~ an ethylene copolymer having a density
of les~ than abou~ 940 kg/m3, the gas composition is
typically from 50 to 60 mole % ethylene, 15 to 25 mole
butene-l with the remainder, apart from inert materials
and impurities, being hydrogen. However, if the monomer
~4~
- 16 - 31124
being polymerised is ethylene only, the amount o~ hydrogen
used may be greater, for example the reaction mixture may
contain in excess o~ 50% molar o~ hydrogen If ethylene is
being copolymerised the proportion o~ hydrogen may be le~s
and typically an amount o~ hydrogen o up to 35~ molar
i8 ~u~ficient. However, it will be appreciated that the
amount o~ chain trans~er agent will be dependent upon the
polymerisation conditions, and especially the
temperature.
The molecular weight distribution (MWD) o~ the
polymer has been ~ound to be dependent, to some extent, on
the nature of component 2) of the catalyst system. In
particular, we have found that the MWD of the polymer is
influenced by the nature of the halogen-containing
compound and the stage at which this is incorporated into
component 2~. Thu~, we have found that using silicon
tetrachloride as the halogen-~ontaining compound, a
polymer having a narrower MWD is obtained than when using
boron trichloride as the halogen-containing compound. The
u~e of other halogen-containing compounds such as
trichlorosilane or phosphorus trichloride also may result
`~ in polymers having a broader MWD than is obtained when
using silicon tetrachloride as the halogen-containing
compound. m ese effects on MWD are most signiicant when
component 2) of the catalyst has been prepared by reacting
the at least one solid particulate material with the
haloyen-containing compound and thereafter reacting the
product obtained, in turn, with ~he other components
(component II and component IV).
In carrying out the process of the present invention,
~he catalyst components may be pre-mixed before they are
introduced into the polymerisation reactor.
Alternatively, the catalyst components may be added to the
polymerisation reactor as separate components. Component
1) o~ the catalyst, which is typically an organic
- 17 - 31124
aluminium compound, may be added to the reactor as a
liquid either as a solution in an inert hydrocarbon
diluent or, if component 1) itself i~ a liquid, aq the
neat undiLuted material. Alternatively, component 1) o
the catalyst may be adsorbed on a suitable support
material which may be an inert organic material such as a
polymer o the type being produced or a so~id particulate
materiaL o the type which is used for the production of
component 2) of the catalyst system.
The catalyst, or catalyst components, may be
introduced into the polymerisation reactor as a suspension
or solution in a suitable inert liquid medium. However,
particularly if polymerisation is being carried out in the
gas phase, and both of the catalyst components are used in
the form o solid materials, the catalyst components may
be added to the polymerisation reactor suspended in a
stream of the gaseous monomer or monomer mixture.
Since the process of producing component 2) of the
catalyst includes a step of treating with an organic
magnesium compound, or a complex or mixture of an organic
magne~ium compound and an aluminium compound, component 2)
of the catalyst may show some polymerising activity,
particularly for ethylene, even in the absence of
component 1) of the catalyst. If component 2) of the
catalyst system possesses polymerisation activity, this
may cause blocking of the catalyst metering or feeding
devices when using a stream of a polymerisable monomer as
the medium for transporting component 2) of the catalyst
system. To avoid this, component 2) may be temporarily
deactivated, or "pacified", by treatment with a suitable
"pacifying agent". Suitable "pacifying agents" include
carbon monoxide, carbon dioxide and also reagents which
remove metal-carbon or metal-hydrogen bonds from the
transition metal composition which is component 2) of the
catalyst system. Typically the "pacifying agent" is a
- 18 - 31124
protic reagent such as a carboxylic acid, an aliphatic
alcohol having rom one up to six carbon atoms or an
anhydrous hydrogen halide. Hydrogen halides, especially
hydrogen chloride, are preferred "pacifying agents".
Using hydrogen chloride, this may be bubbled through a
suspension of component 2) o the catalyst system in an
inert diluent and any excess of the hydrogen chloride can
be removed by sparging with an inert gas such as nitrogen.
The "pacifying agent" is used in a manner, and in
proportion~, such that when the paciied component 2) is
mixed with component 1) an active polvmerisation catalyst
system i9 obtained.
It will be appreciated that the particle form of the
polymer obtained is dependent on, and hence is affected
by, the particle form o the at least one solid
particulate material which is used as component I in the
production of the transition metal composition which is
component 2) of the catalyst system. Hence, by the
selection of a solid particulate material having an
appropriate particle form, such as essentially spherical
particles, a polymer of a desir~d particle orm may be
obtained.
Various aspects of the present invention will now be
described with referance to the following catalyst
preparations and polymerisation Examples, all stages of
which were effected under an atmosphere of nitrogen unless
otherwise indicated.
A) Treatment of alumina
. . _ ~
A sample of hydrated gamma alumina ~Ketjen Grade B
obtainable from Akzo Chemie of Amsterdam, Holland) was
heated up to 700C under a stream of nitrogen at
atmospheric pressure, maintained at 700C for 2 hours
and then allowed to cool, in the oven, to ambient
temperature.
.
o~
- 19 - 31124
B) Treatment of silica
The procedure o~ A) was repeated using silica
(Davison 952 grade obtainable from W R Grace and Company
o~ Maryland, USA).
C) Treatment of silica
The procedure of B) was repeated with the exception
that a temperature of 350C was used.
D) Treatment of alumina
The procedure of A) was repeated with the exception
that a temperature of 500C was maintained for four
hours.
I Preparation of transition metal reaction product
a) Reaction with alumina and 8i licon tetrachloride
29.5 g of the alumina dried as described in
treatment A) were suspended in 300 cm3 of an isoparaffin
raction, essentially all of which had a boiling
temperature in the range from 117C up to 135C, in a
600 cm3 jacketted reaction vessel provided with a
sintered glas~ frit and a stirrer. 3.4 cm3 of silicon
tetrachloride were added to the suspension, whilst
stirring, over a period of two minutesO Stirring was
continued and the mixture was heated to 80C and
maintained at that temperature for 15 minutes. The
mixture was filtered whilst still hot, the solid wàs
25 washed four time- at 80C using 300 cm3 of the
isoparaffin fraction for each wash and the washed solid
was suspended in 300 cm3 of the isoparaffin fraction at
ambient temperatureO
b) Treatment with magnesium dibutyl
To the mixture from Ia) were added 23.8 cm3 of a
0.62 M solution of magnesium dibutyl (an equimolar mixture
of primary and secondary dibutyl magnesium) in the
isoparaffin fraction. This mixture was stirred for
20 minutes at ambient tempera~ure, a further 45 minutes
at 80C and then allowed to cool to ambient temperature.
- 20 - 31124
c) Treatment with titanium tetrachloride
To the reaction mixture from Ib) was added 0.55 cm3
o~ titanium tetrachloride. The mixture was stirred at
amblent temperature for 15 minutes, a ~urther 25 minutes
at 80C and was then allowed to cool to ambient
t:emperature. The solid reaction product present in the
reaction mixture will hereafter be identified as TMC-I.
In the foregoing procedure in step Ia), 1 millimole
of silicon tetrachloride was used for each gramme of
alumina (which contained approximately 1 millimole of
reactive sites per gramme), in step Ib), 0.5 millimole of
magnesium dibutyl was used or each gramme of alumina, and
in step Ic), 0.17 millimole of titanium tetrachloride was
used for each gramme of alumina.
II Preparation of transition metal reaction product
a) Reaction with alumina and silicon tetrachloride
. .
97.4 g of the alumina dried as described in treatment
A) were suspended in lOQ0 cm3 of the isoparaffin
fraction in a two litre jacketted reaction vessel provided
with a stirrer. 16.7 cm3 of silicon tetrachloride were
added to the suspension, whilst stirring, over a period of
; three minutes. Stirring was continued and the mixture was
heated to 80C and maintained at that temperature for two
hours. Stirring was stopped, the mixture allowed to
; 25 se~tle and the supernatant liquid was removed by
; decantation. The ~olid was washed four times at ambient
temperature using 1800 cm3 of the isoparaffin fraction
for each wash and the washed solid was suspended in
1000 cm3 of isoparaffin fraction at ambient
temperature.
b) Treatment with_magnesium dibutyl
To the mixture from IIa) were added 78.5 cm3 of the
0.62 M solution of magnesium dibutyl used in step b) of
preparation I. The mixture obtained was stirred, heated
to 80C, maintained at ~ha~ temperature for one hour and
then allowed to cool to ambient temperature.
- 21 - 31124
c) Treatment with titanium tetrachloride
To the reaction mixture from IIb) were added
5.9 am3 o~ titanium tetrachloride. The mixture was
stirred a~ ambient temperature for 30 minutes. The
mixture was allowed to settle and the supernatant liquid
was removed by decantation. The solid waa washed six
times by decantation using 1500 cm3 of the isoparaffin
fraction at ambient temperature for each wash. The solid
was finally suspended in 1000 cm3 of the isoparaffin
fraction at ambient temperature. The solid reaction
product present in the reaction mixture will hereafter be
identified as TMC-II.
In the foregoing procedure in step IIa), 1 millimole
of silicon tetrachloride was used for each gramme of
alwmina (which contained approximately 1 millimole of
reactive sites per gramme), in step IIb), O.S millimole of
magnesium dibutyl was used for each gramme of al~mina, and
in ~tep IIc), 0.55 millimole of titanium tetrachloride was
used for each gramme of alumina.
III Preparation of transition metal reaction product
The procedure described for preparation II was
repeated with the exception that some of the conditions
were varied and additional treatment steps were added.
In step a), 132.5 g of alumina were suspended in
1500 cm3 of the isoparaffin fraction and 73 cm3 of
silicon tetrachloride were added. The mixture was heated
at 80C for three hours and was then allowed to cool to
ambient temperature~ The mixture was not separated.
After atep a), and before effecting step b), to the
reaction mixture from step a) were added 2.5 cm3 of
titanium tetrachloride. The mixture was stirred at
ambient temperature for one hour, allowed to settle and
the supernatant liquid removed by decantation. The solid
was washed ten times by decantation using 1500 cm3 Of
the isoparaffin fraction at ambient temperature for each
- 22 - 31124
wash. The ~olid was finally resuspended in 1500 cm3 of
the isoparaffin fraction.
In step b) 107 cm3 o the magnesium dibutyl
solution was used and the mixture wa~ ~tirred for one hour
ak ambient temperature.
In step c), 2.S cm3 of titanium tetrachloride were
used, the mixture was stirred for one hour at ambient
temperature and was not subsequently separated. m e solid
reaction product present in the reaction mixture, when
used in a polymerisation process as described in
Example 11, was found to give an active polymerisation
catalyqt system. A portion of the product of step c) was
separated and subjected to a further treatment step.
To this separated portion, which contained 40 g of
solid was added 1.32 cm3 of titanium tetrachlorids. The
mixture was stirred at ambient temperature for one hour
and then filtered. The solid was washed four times using
S00 cm3 of the isoparaffin fraction at ambient
temperature for each wash. The solid was finally
resuspended in 600 cm of the isoparaffin fraction.
The solid reaction product obtained will hereafter be
identified as TMC-III.
IV P~aration of transition metal reaction product
The procedure described for preparation II was
repeated with the exception that some of the condi~ions
were varied.
In step a), 74.6 g of alumina, 1200 cm3 of the
isoparaffin fraction and 4.1 cm3 of silicon
tetrachloride were used. The mixture was stirred at
ambient temperature for 1.5 hours but was not heated to
80~C. The solid was washed three times using 1900 cm3
of the isoparafin fraction and finally resuspended in
1200 cm3 of the isoparaffin fraction.
:`
- 23 - 31124
In step b), 120~3 cm3 of the magnesium dibutyl
solution were added. The mixture was stirred at ambient
temperature for 1~25 hours, heated to 80C and maintained
at that temperature for one hour. The supernatant liquid
was deaanted o, the solid was washed three times by
decantation using 1900 cm3 of the isoparaffin raction
at ambient temperature for each wash and finally suspended
in 1200 cm3 of the isoparaffin fraction.
In step c), 4.1 cm3 o titanium tetrachloride were
added and stirring at ambient temperature was effected for
1.25 hours. The solid was washed twice using 1900 cm3
of the isoparaffin fraction and finally suspended in
1500 cm3 of the isoparaffin fraction.
The solid reaction product obtained will hereafter be
identified as TMC-IV.
V Preparation of transition metal reaction product
To a portion of the suspension obtained in
preparation IV was added titanium tetrachloride in an
amount equivalent to 0.5 millimole of titanium
tetrachloride for each gramme of solid. The mixture was
stirred at ambient temperature for three hour~, allowed to
settle, the supernatant liquid removed by decantation and
the solid washed three times by decantation using
1900 cm3 of the isoparaffin fraction for each wash. The
solid was finally suspended in the isoparaffin fraction to
give a concentration of 1 gramme of solid for each
40 cm3 of li~uid.
The solid reaction product obtained will hereafter be
identified as TMC-V.
VI Pxeparation of transition metal reaction product
The procedure described for preparation I was
repeated with the exception that some of the conditions
were varied.
In step a), 21.7 g of the ilica dried as described
in treatment B) were suspended in 150 cm3 of the
~.~4~
- 24 - 31124
isoparafin fraction. The mixture was heated to 60C and
0.72 cm3 o silicon tetrachloride were added. The
mixture was stirred at 60C for 1 hour 15 minutes. The
solid was washed three times using 75 cm3 o the
isoparain fraction at between 65C and 85C for each
wash. The solid was then suspended in lS0 cm3 of khe
isoparain raction and the mixture allowed to cool to
60~C.
In step b), 36.5 cm3 of the magnesium dibutyl
solution were added followed by 16 cm3 of a 0.62 M
magnesium dibutyl solution in a mixture o hexane and
heptane. This mixture was stirred at 60C for three
hours~ cooled to 25C, filtered and the solid washed three
times using 75 cm3 o the isoparaffin fraction at
ambient temperature for each wash. The solid was finally
suspended in 150 cm3 of the isoparaffin raction.
In step c), the mixture was heated to 70C,
O.9S cm3 of titanium tetrachloride was added and the
mixture was stirred for 65 minutes. The mixture was
~0 filter~d and the solid resuspended in 150 cm3 of the
isoparafin fraction at ambient temperature.
The solid reaction product obtained will hereafter be
identii~d as TMC-VI.
VII Preparation of transition metal reaction product
The procedure described for preparation II was
repeated with the exception that some of the condi~ions
were varied.
In step a), 82.0 g of alumina, 1000 cm3 of the
isoparaffin fraction and 200 cm3 of a 0.62 M magnesium
dibutyl solution in hexane was used (no silicon
tetrachloride was added in this step). The mixture was
stirred or three hours at ambient temperature. The solid
was washed three times using 1900 cm3 of the isoparaffin
fraction for each wash and was suspended in 1300 cm3 of
the isoparain fraction, all at ambient temperature.
~o~
- 25 - 31124
In step b), to the suspension rom step a~ were added
4.5 cm3 of silicon tetrachloride (no magnesium dibutyl
solution was used in this step). The mixture wa~ stirred
at ambien~ temperature for one hour, heated to 80C and
maintalned at that temperature for one hour.
In step c), 4.5 cm3 of titanium tetrachloride
were added to the suspension at 80C from step b). The
mixture was stirred at 8QC for 30 minutes and allowed to
cool to ambient temperature while continuing to stir. The
product was not separated or washed.
The solid reaction product present in the reaction
mixture will hereafter be identified as TMC VII.
VIII Preparation of transition metal reaction product
About 650 cm3 of the suspension obtained in
preparation VII were transferred to a different reaction
ves~el, the liquid was filtered of and 550 cm3 of
titanium tetrachloride were added. The mixture was
stirred, heated to 80C and maintained at that temperature
for 3.5 hours. The supernatant liquid was removed and the
20 solid was washed three times at 80C using 1900 cm3 of
the isoparaffin fraction for ea~h wash, and then three
times at ambient temperature using 1900 cm3 of the
isoparaffin fraction for each wash. The solid was finally
suspended in 800 cm3 of the isoparaffin fraction.
~he solid reaction product obtained will hereafter be
identified as TMC-VIII.
IX Preparation of transition metal reaction product
a) Reaction with alumina and trichlorosilane
50 q of the alumina dried as described in treatment
A) were su~pended in one litre of the isoparaffin fraction
in a two-litre jacketted reaction vessel provided with a
stixrer. 5.5 cm3 of trichlorosilane were added to the
suspension. The mixture was then stirred at ambient
temperature (about 20C) for two and a half hours.
Stirring was stopped, the mi~ture was allowed to settle
11~0~
- 26 - 31124
and the supernatant liquid was removed by decantation.
The solid was washed twice by decantation using 1800 cm3
o~ the isoparafin fraction at ambient temperature for
each wash. A~ter the second wash, most o the residual
liquid was removed by forcing it through a glass tube at
the lower end of which was located a sintered glass frit.
The washed solid was suspended in one litre of the
isoparafin fraction at ambient temperature.
b) Treatment with magnesium dibutyl
To the mixture from step a)~were added 40 cm3 of
the magnesium dibutyl solution used in step b) of
preparation I. This mixture was stirred for 30 minutes at
ambient temperature.
c) Treatment with titanium tetrachloride
. . _ . _ . _ _
To the reaction mixture from step b) were added
3.6 cm3 of titanium tetrachloride. The mixture was
stirred at ambient temperature for 30 minutes, allowed to
stand without stirring for 16 hours and ~hen stirred for a
further one hour. The mixture was allowed to settle and
the supernatant liquid was removed by decantation. m e
solid was washed twice using 15~0 cm3 of the isoparaffin
fraction at ambient temperature for each wash. After ~he
second wash, most of the residual liquid was removed by
forcing it through a glass tube at the lower end of which
was located a sintered glass frit. The washed solid was
finally suspended in one litre of the isoparaffin fraction
at ambient temperature. The product obtained will
hereafter be identified as TMC-IX.
In the foregoing procedure in step a), one millimole
of trichloro ilane was used for each gramme of alumina
(which contained appxoximately one millimole of reactive
sites per gramme~, in st~p b), 0.5 millimole of magnesium
dibutyl was used for each gramme of alumina, and in step
c), 0.17 millimole of titanium tetrachloride was used for
each gramme of alumina.
~.410YI~
- 27 - 31124
X Preparation of transition metal reaction product
a) Reaction with alumina and phosphorus tri hloride
49.3 ~ of the alumina dried as described in
treatment A) were ~uspended in 300 cm3 o the
S i30para~in raction in a two-litre jacketted reaction
ves~el provided with a stirrer. 4.5 cm3 o phosphorus
trichloride were added to the suspension. The m~xture was
then stirred at ambient temperature (about 20C) or four
hours. The mixture was allowed to settle, the supernatan
liquid was removed by decantation and the solid wa~ washed
four times by decantation using 1500 cm3 o the
isoparaffin fraction at ambient temperature for each wash.
The washed solid was suspended in 1000 cm3 of the
isoparaffin fraction at ambient temperature.
b) Treatment with magnesium dibutyl
To the mixture from step a) were added 40 cm3 of
the magnesium dibutyl solution used in step b) of
preparation I. The mixture obtained was stirred for
30 minutes at ambient temperature.
c) Treatment with titanium tetrachloride
~ ~ . .. . . , . . _ _ _ . _ . _ . _
To the reaction mixture fr~m step b) were added
2.75 cm3 of titanium tetrachloride. m e mixture was
stirred at ambient temperature for 30 minutes. The
mixture was allowed to settle and the supernatant liquid
was removed by decantation. The sol.id was washed four
times using 1500 cm3 of the isoparaffin fraction at
ambient temperature for each wash. ~he solid was finally
suspended in 1000 cm3 of the isoparaffin fraction at
ambient temperature. The solid reaction product obtained
will hereafter be identified as TMC-X.
In the foregoing procedure in step a), one millimole
of phosphorus trichloride was used for each gramme o
alumina (which contained approximately one millimole of
reactive sites per gramme), in step b) 0.5 millimole of
3$ magnesium dibutyl was used for each gramme of alumina, and
- 28 - 311~4
in step c), 0.5 millimole of titanium tetrachloride was
used ~or each gramme of alumina.
XI Preparation o~ transition metal reaction product
a) Reactlon with silica and magnesium dibuty~
146 g o~ the silica dried as described in
treatment C) were suspended in 600cm3 of the isoparaffin
fraction in a two~litre jacketted reaction ves~el provided
with a stirrer. 471 cm3 of the solution of magnesium
dibutyl used in step b) of preparation I were added to the
suspension. The mixture was then stirred at ambient
temperature (about 20C) for four hours. Stirring was
stopped, the mixture allowed to settle and the supexnatant
liquid waa removed by decantation. The solid was washed
six times by decantation using 1500 cm3 o~ the
isoparafin raction at ambient temperature for each
wash.
b) Treatment with silicon tetrachloride
The washed solid from step a) was suspended in
729 cm3 of silicon te~rachloride and a quantity of the
isoparaffin fraction was added to give a total volume of
the reaction mixture of 1500 cm3. mis mixture was
stirred, heated to 80C and maintained at that temperature
- for four hours. The mixture was then allowed to settle,
the supernatant liquid was decanted off and the solid was
waqhed nine times u~ing 1500 cm3 of the isoparaffin
fraction at ambient temperature for each wash. After the
final wash most of the liquid was removed by forcing it
through a glass tube at the lower end of which was located
a sintered glass frit.
c) Treatment with titanium tetrachloride
.. . ..
The washed solid from step b) was suspended in
1460 cm3 of titanium tetrachloride . The mixture was
stirred, heated to 80C and maintained at that temparature
for four hours. ~le mixture was allowed to settle, the
supernatant liquid was decanted of~ and the solid was
- 29 - 31124
washed by decantation six times using 1500 cm3 of the
isopara~fin fraction at 80C for each wash and a further
our times using 1500 cm3 o the isoparaffin fraction at
ambient temperature or each wash. The solid wa~ finally
suspended in the isoparafin fraction at ambient
temperature to give a total volume of 1500 cm3~ The
solid reaction product obtained will hereafter be
identified as TMC~XI.
In the foregoing procedure, an excess quantity of
each o the reactants, relative to the silica, was used.
The products of prepara~ions I to XI were used to
efect the copolymerisation o~ ethylene with a l-olefine
monomer as described in the following Examples.
XAMPLES 1 T0 10
Into a stirred stainless steel autoclave of 30 litres
capacity were introduced, under hydrogen at a pressure of
4.2 kg/cm2 gauge, 13 litres o a mixture of hexane
and but~ne-l. The mixture also contained 40 millimoles of
aluminium trioctyl and 50 ppm by weight of an antistatic
agent of the formula C6F13(CH2CH2)gCnH(2n~1) where n
a value of rom 16 to 18~ -
The contents of the reactor were stirred and heatedup to 80C. The reactox was vented to reduce the
pressure. Ethylene was added to give a total pressure of
80 psi gauge ~5.6 kg/cm~ gauge). A titanium-containing
component was then added in a quantity to attain, and
Rubsequently to maintain, a monitored ethyLene consumption
of between 1.0 and 1.5 kg per hour. Ethylene was added at
a rate suficient to maintain the pressure of 80 psi gauge
(5.6 kg/cm2 gauge). During the reaction, unless
otherwise indicated, a 0.1 M solution o~ aluminium
trioctyl in hexane was added continuously at a rate of
40 millimoles per hour.
~4~
~ 30 - 31124
The polymerisation was terminated and the polymer
product consequently recovered by trans~erring to a ves.~el
of ~00 litre~ capacity containing 50 litres of a 0.01 N
aqueous solution o.~ sodium hydroxide and then passing
S ~team through the stirred mixture until all o~ the hexane
had been evaporated~ The aqueous polymer suspension was
then ~iltered and the polymer was dried in a fluid bed
drier using hot nitrogen as the fluidising gas.
Further details of the polymerisations, and the
re~ults obtained, are set out in Table I.
~ 31 - 31124
. .. . .
:4-- CO ~7 lO a~ N ~J ~ U~ N
F~ r) u~ u~ ul ~ ~r ~ u U)
_ ~ i
, ____ - .. ~
tn u~ o o o o o o o o o
-~ S ~î ~ O ~ O
t~ ~ i ~i r`i ~i N -i
._ .. _ .... __ . _
~ ~_ ~ 0 _1 ~ In ~ u~ ~g
U~ N ~9 0
~ _ --I O ~ I N
_ .. .-.
~ j~)
!~ .c ~ ~ o co d' I~
1~ _ ~ ~ a~ N N N _I
. .. -.~ -- ~
a) I~ l ~ o ~D CO
~ ~ o co a~
o ~ ~ o o o -~ o ~ ~
` a~l ,.. . _. .
~ o
E~ ~ _
~1 ~ 1~ ~ ~ ~ ~ ~ ~ ~ ~ ~
--I ~ _ N N N N N N N N N N
,~ X
H
' . . _ ..
~_ ~r ~ o ~ o o 0 ~ ~ o
~ O ~) O ~ O O ~ O
., 0~ a~
~ ~
~ ~_ u7 ~
Q o u ~ u~ r-l o N ~ i
C~ 11-~ H ~ ~ H H 1-1 X X H
5 IY ~2 H H ~ ~ H l--I X
.._____ .._ ~ _.
~ ~05 0 --I N ~ ~ In ~ 1` 0 Ci~ O
. -- ~_ ~
- 32 - 31124
Notes to Table 1
(a) In the Examples marked *, 200 millimoles of
aluminium trioctyl were present in the i~itial
reaction mixture and no urther alumini-~ trioctyl
was added during the course o the polymerisation.
~b) As defined in Preparations I to XI.
(c) is given as total mM of titanium contained in the
product of Preparations I to XI which was added to
initiate and maintain the polymerisation.
(d) Expressed as
(Wt butene-l) x 100
Wt initial mixture of butene-l plus hexane
(e) This is the pressure to which the reactor was vented
before adding the ethylene.
(f) MFI is melt flow index measured by ASTM Method D
1238-70 at 190C using a 2.16 kg wei~ht.
(h) Density was measured as described in ASTN 1928/70,
Method A, using a density gradient column at 23C.
(i) Figures af~er the decimal point equal minutes, that
is l.I0 means 1 hr 10 minutes.
(j) S.Ex. is stress exponent and is given by the
relationship.
~10 MFI 5 - Log10 MFI-2.16
Log10 5 - Log10 2.16
2S where MFI 5 is the melt flow index mea~ured as in
(f) using a 5kg weight and MFI 2.16 is the melt flow
index measured as in (f).
EXAMPLE 11
A 20 cm internaL diameter fluidised bed reactor
vessel, operated in a continuous manner, was used to
produce an ethylene/butene-l copolymer. A reaction
mixture comprising ethylene, butene-l and hydrogen was
circulated continuously through the bed at a superficial
velocity estimated to be about four times the
~09~ :
- 33 - 31124
minimum necessary for fluidisation. In the fluidi3ed bed,
the reactlon temperatuxe was controlled at 80C by
adjusting the temperature of the ga~ fed to the fluidised
bed reactor vessel using a heat exchanger in the
S circulating gas loop. Aluminium trioctyl was pumped
continuously into the reactor as a 0.25 molar solution in
n-hexane. The solid reaction product TMC II was blown
into the reactor as a dry powder in a stream of process
gas at frequent intervals so as to maintain a rate of
polymer production of about 1.5 kg/hr, which corresponds
to a mean residence time of four hours. The reaction
pressure was maintained automatically by admitting an
ethylene/hydrogen mixture through a control valve. Liquid
butene-l was pumped into the circulating gas stream so as
to maintain a constant composition as determined by 5as
Liquid Chromotography.
The polymer formed was removed periodically so as to
maintain an essentially constant level in the reactor
vessel. m e polymer collected was degassed in a stream of
nitrogen which had been passed over a bath of water at
ambient temperature, and then through a steam jacket. The
use of this warm, moist nitrogen removed monomers and al~o
de-activated the catalyst and alkyl residues~
Further details, together with some characteristics
of the polymers obtained, are set out in Table 2.
- 34 - 31124
,
_
. U~
~ ~ .~ .
. ~_ ,i
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~ ~ ~ ~q ~
~ ~ ~ ~ ~ ~ ~
n ,~ ~ . s~
u ~n ~ o . ~ s~ o
~ q CD O ~
,~ h--,~3 ~ ~ U
. ,1
....... _. _
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,1 ~ ~ ~ ~ ,~
O a~,Y O~
C~
__ __ ~
Ll o O
_1 ,0 ~ _~
!~ ~n
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O .,~
111 :~
- .. _ _ _ ~ O ~
~ ~ ~ O
O Q)-rl ).1 .,1 ~ ~
~ ~ CO ~ ~q
_l a) ~ ~ I ~`I Q~
~ ~ ~1 ~ Cll-- . ~ ,1 0
E1 ,~ ~ o _l tq
P~ n~
_ r~ r~
~ ,~
~ ~ ~ 0
O _ ,~ a~ ~
~rl X -- ~ ~U
.,, I . rl ~q
` ~ O w :n ~ _
~: ~ _ ~
: ` ~ ~ ~ ~ :
` ~ ~ ~ U~ ~ ~ ~
_ ~ r~
r~ s~
~ ~ ~ u~ ~
, ~5 ~`I ~ O ~ 0 la
K 13 a~
.- - . .__ . _ ,~ _ ~ ~ ~ ~
H ~ U ,8 -- Sl U~ $
H Q~ 0 ~ Ul Ul ~rl
~ ~ O ~ ~rl ~rl Ul L
C~ . O ~
æ P; ~ ~ o ~ u s
E~ ~, ~
_ rn ~ O
X o _l ~ ~ ~ ~
~ ,~z _, Zo ~ X ~'
~L~4~;D9i
~ 35 ~ 31124
XII Preparation of transition metal reaction product
a) Reaction with silica and magnesium dibutyl
10.6 g of the silica dried as described in treatment C)
were suspended in 100 cm o~ a heptane fraction,
essentially all of which had a boiling point in the range
99C up to 102aC ~hereater re~erred to simply as the
"heptane fraction") in a 200 cm3 three ne~ked glass
flask provided with a glasq frit and a stirrer. 45.1 cm3
of a 0.705 M solution, in the isoparaffin fraction, of the
magnesium dibutyl used in step b) of preparation I were
added to the suspension. The mixture was stirred, heated
to 70C and maintained at that temperature for one hour.
Stirriny was stopped, the mixture was allowed to settle
and the suparnatant liquid wa~ removed by filtration. The
solid was washed 5 times by filtration using 100 cm3 of
the heptane frac~ion at ambient temperature for each wash.
The damp solid was dried at ambient temperature at a
pressure of 5 mm of mercury until it became a free flowing
powder.
b) Reaction with titanium tetrachloride/carbon
.
tetrachloride
The dried solid obtained in stage a) was transferred,
in portions, through a flexible PVC tube into a similar
200 cm3 three necked glass flask containing a stirred
mixture o 72 cm3 of titanium tetrachloride and 28 cm3
of carbon tetrachloride at ambient tempera~ure. The
contents of the reaction vessel were then stirred for one
hour at ambient temperature. The supernatant liquid was
removed by fil ration and the solid was washed 8 times by
filtration using 100 cm3 of the heptane fraction at
ambient t~mperature for each wash. ~he solid was finally
suspended in a total of 500 cm3 o the heptane
fraction.
The solid reaction product obtained will hereafter be
identified as TMC-XII.
~41~1
- 36 - 31124
XIII Preparation of transition metal reaction ~roduct
a) Reaction with silica and magnesium dibutyl
The procedure o qtage a) of preparation XII was
repeated using 9.81 g of silica and 41.7 cm3 of the
magnesium dibutyl solution.
b) Reaction with titanium tetrachloride/carbon tetra-
~ ... = .... .. ... . .... _ ... .
chloride mixture
The procedure of staye b) of preparation XII wasrepeated u9ing a mixture of 65 cm3 of titanium
tetrachloride and 35 cm3 of carbon tetrachloride.
The solid reaction product obtained will hereafter be
identiied as TMC-XlII.
XIV Preparation of transition metal reaction product
a) Xeaction wlth ~ilica and ma~nesium dibutyl
The procedure of stage a) of preparation XII was
repeated using 10 g of silica and 42.5 cm3 of the
magnesium dibutyl solution.
b) Reaction with titanium tetrachloride/carbon tetra-
_ .
chloride _ixture
The procedure of stage b) of preparation XII was
repeated with the exception tha~, after adding the solid
to the liquid mixture, the contents of the reaction vessel
were heated up to 80C and maintained at that temperature
for four hours. Subsequently, the solid was washed 8
times with the heptane fraction at 80C.
m e solid reaction product obtained will hereafter be
identified as TMC-XIV.
XV and XVI Preparation of transition metal reaction
products
a) Reaction with silica and boron trichloride
__ _
Into a 250 cm3, three necked, round-bottom flask
provided with a magnetic stirrer were placed 18.64 g of
the silica dried as described in treatment C). To one
neck of the flask were connected a cold finger containing
an acetone/solid carbon dioxid~ mixture. The cold finger
~L:41~9~L
- 37 - 31124
was also connected to a container of boron trichloride~
The whole sy~tem was evacuated to a residual pressure o
about 0.1 mm o mercury. The boron trichloride vaporised,
aondensed on tha cold finger and dripped into the flask
containing the silica.
The contents of the round-bottom flask were agitated
for three hours, using the magnetic stirrer and manual
haking. During this time the contents of the cold finger
were removed and the cold finger was allowed to warm up to
ambient temperature. m e boron txichloride container was
replaced by a bubbler containing BDH liquid paraffin. At
the end of three hours, nitrogen was passed into the round
bottomed flask to raise the pressure to atmospheric and
the nitrogen was passed through the bubbler for five
minutes in order to remove any unreacted boron trichloride
~rom the Rilica.
XVb) Treatment wlth magnesium dib~yl
6.23 g o the solid reaction product rom step a)
were placed in a 200 cm3 three necked glass flask
provided with a glass frit and a stirrer. 50 cm3 of the
heptane fraction were added to the flask followed by 17.2
cm3 of a 0.618 M solution of the magnesium dibutyl in
the isoparaffin fraction. m e mixture was stirrer for one
hour at ambient temperature. The mixture was filtered,
and washed five times using 100 cm3 of the heptane
fraction at ambient temperature for each wa~h.
XVc) Treatment with titanium tetrachloride
To the solid from step XVb) were added 100 cm3 of
tithnium tetrachloride. The mixture was stirred, heated
up to 80C and maintained at that temperature for four
hours~ me mixture was filtered, washed 8 times using
100 cm3 of the heptane fraction at 80C for each wash
and finally suspended in 100 cm3 of the heptane fraction
at ambient temperature. The mixture was transferred to a
storage vessel and a fur~her 150 cm3 of the heptane
fraction were added.
~L
- 38 - 31124
The solid reaction product obtained will hereafter be
identified as TMC XV.
XVIb) Treatment with ma~nesium dibutyl
The pxocedure described in step XVb) was repeated
using 6.81 g o the solid reaction product ~rom step a)
and 18.8 cm3 o the magnesium dibutyl solution.
XVIc) Treatment with titanium tetrachloride
To the solid from step XVIb) were added 50 cm3 of
the heptane fraction and 0.64 cm3 of titanium
tetrachloride. m e mixture was stirred for two hours at
ambient temperature, filtered, the solid was washed once
with 100 cm3 o~ the heptane fraction at ambient
temperature and suspended in 100 cm3 of the heptane
fraction at ambient temperature. The mixture was
transfarred to a storage vessel and a urther 150 cm3 of
the heptane fraction were added.
The olid reaction product obtained will hereafter be
identified as TMC XVI.
XVII Preparation o transition metal reaction Rroduct
a) Reaction with alumina and ma~nesium dibutyl
11.5 g of the alumina dried as described in treatment
D) were placed in a 200 cm3 three necked glass flask
provided with a glass frit and stirrer. 50 cm3 of the
heptane fraction were added and the mixture was stirred.
55.8 cm3 of an 0.618 M solution of the magnesium dibutyl
were added and the mixture was stirred for one hour at
ambient temperature. m e mixture was filtered~and the
solid was washed five times using 100 cm3 of the heptane
fraction at ambient temperature for each wash.
b) Treatment of boron trichloride
,~ ~
7.5 cmJ of liquid boron trichloride were evaporated
on to the damp solid obtained in step a) using the
procedure described in step a) of preparations XV and XVI.
The mixture was allowed to stand for three hours. The
solid wa~ washed five times using 100 cm3 of the heptane
fraction at ambient temperature or each wash.
~41~91
- 39 - 31124
c) Treatment with titanium tetrachloride
_ ", . . .
The solid from step b) was suspended in 100 cm3 of
titanium tetrachloride, the mixture was stirred, heated to
80C and maintained at that temperature for four hours.
The mixture was iltered and the solid was washed 8 times
using 100 cm3 of the heptane fraction at ambient
temperature or each wash. The solid was suspended in 100
cm3 of the heptane fraction, transferred to a storage
vessel and a further 150 cm3 of the heptane fraction
were added~
The solid reaction product obtained will hereafter be
identified as TMC-XVII.
XVIII Pre~?aration of ~ e ~ct
a) Reaction with alumina and magnesium dibutyl
.
The procedure of step a) of preparation XVII was
repeated using 12.91 g of the alumina dried as described
in treatment A), 50 cm3 of the heptane fraction and 62.7
cm3 of the magnesium dibutyl solution.
b) Treatment with boro_ichloride
The damp solid from step a) was treated with 8~4
cm3 of boron trichlorid~, the procedure otherwise being
as described for step b) of preparation XVII.
c) Treatnlent with titanium tetrachloride
.
The solid from step b) was treated with titanium
tetrachloride and washed using the procedure of step c~ of
preparation XVII.
The solid reaction product obtained will hereafter be
identified as IMC-XVIII.
XIX Preparation of transition metal reaction product
.
a) Reaction with alun:ina and ma~nesium dibutyl
The procedure was as described for step a) of
preparation XVIII with the exception that 10.72 g of
alumina, 50 cm3 of the heptane fraction and 52 cm of the
magnesium dibutyl solution were used.
~4~09~ i
- 40 - 31124
b) Treatment with boron trichloride
The damp solid from step a) was treated with 7.0
cm3 o boron trichloride, the procedure otherwiqe being
as described or step b) of preparation XVII.
c) Treatment with titanium tetrachloride
.
The solid from step b) wa~ suspended in a solution of
0.6 cm3 of titanium tetrachloride in 100 cm3 of the
heptane fraction. ~he mixture wa~ stirred for two hours
at ambient temperature, filtered and the solid was washed
twice u~ing 100 cm3 of the heptane fràction at ambient
temperature for each wash. The solid was suspended in
100 cm3 o the heptane fraction, transferred to a
~torage vessel and a further 150 cm3 of the heptane
fraction were added.
The solid reaction product obtained will hereafter be
identified as TMC-XIX.
XX Preparation of transition metal reaction product
a) Reaction with alumina and magnesium dibutyl
85.3 g of the alumina dried as described in treatment
A) were suspended in 870 cm3 of the isoparaffin ~raction
in a ~wo litre jacketted reaction vessel provided with a
stirrer. 132 cm3 of a 0.646 M ~olution, in the
isoparaffin fraction, of the magnesium dibutyl used in
step b) of preparation I wexe added to the ~uspension.
The mixture was stirred at ambient temperature for 30
minutes.
b) Treatment with titanium tetrachloride
To the stirred suspension from step a) were added 4~7
~m3 of titanium tetrachloride over a period of four
minutes. The mixture was stirred for one hour at ambient
temperature. The mixture was allowed to settle and th~
supernatant liquid was removed by decan~ation to give a
final total volume of 780 cm3.
- 41 - 31124
c3 Treatment with silicon tatrachloride
To the stirred suspension from step b) were added
180 cm3 of silicon tetrachloride. The mixture was
~tirred, heated to 80C and maintained at that temperature
for 3 hours. The mixture was allowed to settle and the
supernatant liquid Wa5 removed by decantation. The solid
was wa~hed 9 times using one litre of the isoparaffin
fraction at ambient temperature for each wash. The solid
was finally suspended in 850 cm3 o the isoparaffin
~raction at ambient temperature.
The solid reaction product obtained will hereafter be
identified as TMC-XX.
In the foregoing procedure in step XXa), one
millimole of magnesium dibutyl was used for each gramme of
alumina, in step XXb), 0.5 millimole of titanium
tetrachloride was used for each gramme of alumina and in
step XXc), an excess quantity o silicon tetrachloride,
relative to the reactive sites on the alumina, wa~ used.
EXAMPLES 12 TO 20
The products of preparations XII to XX were used to
effect the copolymerisation of ethylene and butene-l using
the procedure described for E~ample~ 1 to 10.
Further details of the polymerisations, and the
results obtained, are set out in Table 3.
- 42 - 31124
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