PROCESS FOR THE MANUFACTURE OF A CATALYST

PROCEDE DE FABRICATION D'UN CATALYSEUR

English Abstract

Abstract of the disclosure:
A catalyst of high activity and stereospecificity in
.alpha.-olefin polymerization is obtained when titanium trichloride,
prepared from titanium tetrachloride by reduction with an
aluminum alkyl halide, is treated first with an ether and
then, without separation of the ether, with an aluminum alkyl
halide, optionally in the presernce of a small amount of a cyclo
polyene and/or an olefin. With the catalyst obtained high space-
time yields of .alpha.-olefin polymers and copolymers can be produced.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of a catalyst in which
(1) an aluminum dialkyl chloride having alkyl groups of 1 to 6
carbon atoms or an aluminum alkyl sesquichloride is added to
titanium tetrachloride at a temperature of from -20 to +20°C
in a molar proportion of aluminum dialkyl chloride to titanium
tetrachloride of from 0.8:1 to 1.5:1,
(2) the resultant product is separated, (3) the separated pro-
duct is washed, (4) a suspension of washed product in a hydro-
carbon solvent is subjected to a thermal treatment at a temper-
ature of from 40 to 150°C in the presence of a dialkyl ether
and (5) the product is treated with an aluminum alkyl halide.


2. A process as claimed in claim 1 in which in step (5)
the suspension is also treated with at least one member of the
group of cyclopolyenes and olefins.


3. A process as claimed in claim 1 in which in step (1)
the aluminum dialkyl chloride is added to the titanium tetra-
chloride at a temperature of from 0 to 5°C in a molar pro-
portion of from 0.9:1 to 1.1:1.


4. A process as claimed in claim 1, claim 2 or claim 3
in which in step (4) the suspension is subjected to a thermal
treatment at a temperature of from 40 to 100°C in the presence
of a dialkyl ether selected from the group of dialkyl ethers


31



having from 2 to 5 carbon atoms in each alkyl group.


5. A process as claimed in claim 1, claim 2 or claim 3
in which in step (5) the alkyl halide is an alkyl halide of
the formula A1RnX3-n wherein R represents an alkyl radical
having from 2 to 8 carbon atoms, X represents a halogen atom
and n is a number from 1 to 2 and the treatment is carried out
at a temperature of from 0 to 60°C.


6. A process as claimed in claim 1 or claim 2 in which
in step (5) the alkyl halide is selected from the group of
aluminum diethyl chloride, aluminum ethyl dichloride and
aluminum ethyl sesquichloride and the product is also treated
with at least one member of the group of cyclopolyenes selected
from the group of norcaradiene, cyclopolyenes having 7 ring
members and 3 non-cumulated double bonds in the ring and cyclo-
polyenes having 8 ring members and 3 or 4 non-cumulated double
bonds in the ring, and the alkyl and alkoxy-substituted derivatives
thereof and (b) olefins selected from the group of mono-
olefins having 2 to 10 carbon atoms.


7. A catalyst for the polymerization of olefins, whenever
prepared according to a process as claimed in claim 1, claim 2
or claim 3.


8. A process for the preparation of a homopolymer of an
?-olefin of the formula CH2=CHR wherein R is an alkyl radical
having from 1 to 8 carbon atoms, a copolymer of said ?-olefins
with one another and copolymers of said ?-olefins with ethylene,
in which the olefins are subjected to polymerization at a temp-
erature of from 20 to 120°C and at a pressure of from 1 to 50


32

kg/cm2 in the presence of a catalyst prepared by a process in
which (1) an aluminum dialkyl chloride having alkyl groups of
1 to 6 carbon atoms or an aluminum alkyl sesquichloride is added
to titanium tetrachloride at a temperature of from -20 to +20°C
in a molar proportion of aluminum dialkyl chloride to titanium
tetrachloride of from 0.8:1 to 1.5:1, (2) the resultant product
is separated, (3) the separated product is washed, (4) a sus-
pension of the washed product in a hydrocarbon solvent is sub-
jected to a thermal treatment at a temperature of from 40
to 150°C in the presence of a dialkyl ether and (5) the product
is treated with an aluminum alkyl halide.


9. A process as claimed in claim 8 in which in step
(5) the suspension is also treated with at least one member of
the group of cyclopolyenes and olefins.


10. A process as claimed in claim 8 in which the ?-olefin
is propylene.


11. A process as claimed in claim 8, claim 9 or claim
10 in which the monomer is a mixture of propylene with 0.5 to
25% ethylene.


33

Description

HOE 74/F o64
1063~;i88
The present invention relates to a process for the manu-
facture of a catalyst suitable for the polymeri~ation o~ ~-
olefins.
In the polymerization of propylene or higher ~olefins
- 5 with Ziegler type catalysts there are obtained~ besides the
technically very interesting highly crystalline polymers,
which are insoluble or sparingly soluble in the hydrocarbons
- used as dispersion media under the polymerization conditions,
also amorphous, readily soluble polymers, and oils. Accord-
ing to Natta, the highly crystalline polymers are sterically
ordered and are called "isotactic", wh~le the soluble polymers
are sterically disordered and are called "atactic'~.
The formation of isotactic and amorphous poly-~-olerins
i8 regulated by the catalyst system. For an economically u~e-
ful process catalyst system~ having a selectlve action are re-
quired which lead exclusively or almost exclusively to the
formation of the desired polymers.
A process has become known (Brltish patent 895~595) ac-
cording to which the selectivity of catalysts of the afore-
said type can be considerably improved with respect to the
~ormation of polymers with high content of isotactic fraction
by oub~ecting the reaction product of TiC14 and halogen-con-
taining aluminum-organic compounds to a thermal treatment at
; a temperature in the range of from 40 to 150 C and after the
treatment optionally washing the product several times with an
; inert solvent. This heat treated and washed catalyst is then
activated in the elefin polymerization with fresh diethyl alu-
mlnum monochlorlAe. The qfficlency of the hoat troated cQta-
ly~ts can be further improvsed by ert`-~ctin~ th~ therm~l treat-

- 2 -
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ment in the presen~e of complex forming compound~ or compounds
forming double salts, for oxamp]e ethers and ~odium chloride.
There have al~o been de~cribed catalytic complexe~ hav-
ing a high activity and stereospecificity in the polymeriza-
S tion of d-olefin~ (cf. ~erman Offenlegungsschrift 2~213~086).
These complexes are formed by reduction of titanium tetra-
chloride with an aluminum-organic compound, thermal treatment
of the solid reaction product in the reaction medium, separa-
tion of the solid and treating it with an electron donor~
especially an ether, preferably dii oamyl ether, washing the
reaction product and reacting it with titanium tetrachloride.
The catalytic complexes are isolated by a third washing pro-
cess. The preparation of the catalytic complexes is thu~
rather complicated and expensive as large amounts of wash ~o-
lution~ have to be worked up (cf. published documents of Bel-
gian Patent 784~495). In the working up of the wash solutions
to recover the ether, large amounts of titanium-containing
wa~te water are obtained.
The present invention provides a process for the manu-
facture of a catalyst suitable for ~-olefin polymerization by
reacting titanium tetrachloride in an inert hydrocarbon ~ol-
~ent with an aluminum-organic compound containing an aluminum
dialkyl chloride, 3eparating and washing the reaction product
and thermally treating the reaction product su~pended in the
hydrocarbon solvent in the pre~ence of an ether (component A),
mixing with an aluminum dialkyl halide (component B~ and op-
tionally wlth a cyclopolyene a~ ~tereoregulator (component C),
which compriYe~ adding the aluminum-organic compound contain-


i;

ing aluminum dialkyl chloride to the TiCl4 at a temperature


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HOE 74/F o64 K
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of from -20 to +20 C in a molar proportion of aluminum dialkyl
chloride to TiC14 of from 0.8 : 1 to 1.5 to 1, sub~ecting the
suspension containing the ~olid washed reaction product to a
thermal treatment in the presence of a dialkyl ether and after-
~ 5 treating the suspension with an aluminum alkyl halide without
separation of the ether or one of the reaction products.
The invention also relates to the catalyst prepared by
the afore described proces~ and to lts use in the polymeriza-
tion of OC-olefin~.
To prepare the catalyst in accordance with the invention
titanium tetrachloride is first reacted in an inert hydrocar-
bon solvent with an aluminum-organic compound containlng an
aluminum dialkyl chloride.
The aluminum-organic compound containing an aluminum
t5 dialkyl chloride to be used ls either an aluminum dialkyl
chloride carrying alkyl group with 1 to 6 carbon atoms, pre-
;~ ferably aluminum diethyl chloride~ dipropyl chloride~ diiso-
propyl chloride, diisobutyl chloride, more preferably aluminum
diethyl chloride, or an aluminum alkyl sesquichloride, i.e. an
equimolecular mixture of aluminum dialkyl monochloride and
aluminum alkyl dichloride, preferably aluminum ethyl sesqui-
chloride, propyl se~quichloride, isopropyl sesquichloride, or
.
isobutyl sesquichloride, aluminum ethyl sesquichloride being
particularly preferred.
In the reaction of titanium tetrachloride and the alu-
minum-organic compound containing an aluminum dialkyl chloride
the molar proportion of aluminum dialkyl chloride to titanium
tetrachloride is in the range of from 0.8 to 1.5 : 1, pre-
ferably ~.9 : 1 to 1.1 : 1. The aluminum compound 1 9 added

_ 4 --


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HOE 74/F o64 K
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to the dissolved titanium tetrachloride at a temperature of
from -20 to +20 C, preferably O to 5 C.
As solvent an alkane or cycloalkane that is liquid at the
reaction temperature is preferably used, for example hexane,
heptane, octane~ cyclohexane, or a hydrocarbon mixture, for
example a gasoline fraction boiling in the range of from 130
to 170 C. Further suitable ~olvents are those which are used
as dispersion medlum in the polymerization of ~-olefins. The
amount of solvent is preferably chosen in such a manner that a
40 to 60 h by weight solution of the titanium tetrachloride
and a 15 to 25 ~ by weight solution of the aluminum-organic
compound are used.

... .
The formed TiC13-containing solid reaction product i~
separated and freed from all soluble components by washing with
the solvent used.
The reaction product is then again suspended in the sol-
vent in an amount such that the concentration of titanium in
the suspension i~ in the range of from 0.5 to 2.5 moles of
TiCl3, preferably 1.5 to 2.2 moles, per liter of solvent, and
~ub~ected to a thermal treatment in the presence of a dialkyl
ether. The thermal treatment is carried out at a temperature
of from 40 to 150 C, preferably 40 to 100 C and especially
60 to 90 C. Suitable dialkyl ethers are those having from
2 to 5 carbon atoms in each alkyl group, for example diethyl
ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether,
diisobutyl ether, preferably di-n-butyl ether. The molar pro-
portion of titanium trichloride to dialkyl ether in the ther-
mal treatment is preferably in the range of from 1 s o.6 to
1 s 1.2, more pref`er~bly 1 ~ 0.9 to 1 s 1.




- 5 ~




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HOE 74/F o64 K
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The dialkyl ether is added to the ~uspension of the
solid reaction product or vic~ ~ersa. In the heat treatment
the dialkyl ether can be dissolved in a solvent, it is more
advantageous, howe~er, not to dilute it, The dialkyl ether
i~ added to the suspension or the sugpen~ion to the dialkyl
ether at the temperature of the heat treatment over a period
of a few second~ to 5 hours, preferably 1 to 30 minute~. After
mixing of the reaction components, the mixture i9 stirred for
5 to 300 and preferably 30 to 60 minutes at the tempe~ature of
the thermal treatment.
1`he suspension is then treated, without prior separation
of the ether or any of the reaction products~ with an aluminum
alkyl halide. To this effect aluminum alkyl halides of the
formula AlRnX3 n in which R stands for an alkyl radical having
from 2 to 8 carbon atoms, X represents a halogen atom and n is
a number in the range of from 1 to 2 can be used~ preferably
aluminum dialkyl halides, aluminum alkyl dihalides, and alumi-
num alkyl ~esquihalides, more particularly aluminum diethyl
chloride~ aluminum ethyl dichloride and aluminum ethyl sesqui-

chloride. A very economic method consists in using the motherliquor obtained in the preparation of the TiCl3-containing re-
action product and preponderantly containing aluminum alkyl
dichlorides.
The molar proportion of aluminum alkyl halide to TiCl3
2~ in the suspension to be treated is in the range of from 0.8 :
1 to 10 : 1 and preferably 1 : 1 to 5 : 1 and the treatment is
carried out at a temperature of from O to 60 C, preferably
20 to 40 C while stirring.
The after-treatment with the alkyl aluminum halide is




-- 6 --
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. HOE 74/F o64 K
~--' 1063588
preferably carried out in the pres~nce of a small amount of a
cyclopolyene Suitable cyclopolyenes are norcaradiene and
tho~e having 7 rin~ members and 3 non accumulated double bonds
in the ring as well as those having 8 ring members and 3 or 4
non accumulated double bonds in the ring, preferably cyclo-
heptatriene-1,3~5~ cyclooctatriene-1,3~5, and cyclooctatetra-


.;
ene-1,3,5,7 as well as the alkyl- and alkoxy-substituted deri-
vatives thereof in which the alkyl group contains from 1 to 4
carbon atoms, cycloheptatriene-1,3,5 being preferred.
The molar proportion of titanium trichloride to cyclo-
polyene is in the range of from 1 : 0.001 to 1 : 1, prefer-
ably 1 : 0.005 to 1 : 0.8 and especially 1 : 0.075 to 1 : 0.5.
When the after-treatment with an aluminum alkyl halide
is carried out in the presence of a cyclopolyene the addition
of a third catalyst component (component C) in the polymeriza-
tion can wholly or partially be di~spensed with.
The after-treatment with the aluminum alkyl halide can
al~o be carried out in the presence of a small amount of an
olefin, elther in the presence or in the absence of a cyclo-

polyene as defined abo~e. There can be used mono-olefinc hav-
ing from 2 to 10 carbon atoms, preferably ethylene, propylene,
butene-1, or 4-methyl-pentene-1. The molar proportion of ti-
tanium trichloride to olefin is in the range of from 1 : l to
1 : 100, preferably 1 : 1 to 1 : 50 and more preferably
1 : 1.5 to 1 s 20.
When the after-treatment is carried out with an aluminum
alkyl dihalide or aluminum alkyl sesquihalide the catalyst
component A formed mu.st be ~eparated from the suspension and

washed with an lnert hydrocarbon solv-~nt. Wlth the use of ~n



_ 7 _


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` HOE 74/F o64 K
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aluminum dialkyl monohalide, however, the isolation and washing
of component A can be dispensed with. Moreover, in the latter
c~se the amount of catalyst component ~ could be reduced by the
amount o~ aluminum dlalkyl monohalide used for the after-

treatment. -
After separation from the solvent by decantation or fil-
tration, the catalyst component A can be dried with the exclu-
sion of air and humidity and then stored.
Component A is used either in the form of a suspenRion,
for example a~ obtained in the after-treatment with an alumi-
num alkyl halide, or it i9 isolated, washed, suspended in an
inert hydrocarbon solvent and used together with an aluminum
dialkyl halide (component ~) in the polymerization of ~-ole-
fins. It i9 also possible~ of course, to use the dried cata-

ly9t component A per se. O~-Olefins which can be polymerized
with the catalyst of the invention are those of the formula
CH2=CHR in which R stands for an alkyl radical having from
1 to 8 carbon atom~, preferably propylene, butene-1, pentene-1,
3-methylbutene-1, 4-methyl-pentene-1 and 3-methyl-pentene-1,
propylene being preferred. The catalyst according to the in-
vention can be used for the homopolymerization as well as for
. .
the copolymerization of mixtures of the aforesaid olefin6 with
one another and/or with ethylene. In ths copolymerization the
mixture contains at least 95 ~ by weight of one of the ~-ole-

fins and at most 5 D~ by weight of ethylene, each time calcu-
lated on the total amount of bhe monomers. The catalyst is
especially favorable for the polymerization of mixtures of

propylene with small amounts of ethylene of from 0.5 to 5 and
preferably 1.5 to 3 D/D by weight. The catalyst of the invention



-- 8 --

. _ _ _ _ _ .. .. . .. . . .. . . ....... . ... ..

., .~ .

HOE 74/F /64 K
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can also be used for the block polymerization of the said ~-
olefins with one anoth~r and/or with ethylene. In this case
the content of athylene i9 below 25 ~ by weight. Block poly-
mers of propylene and ethylene are preferably made. The block
polymers made with the catalyst of the invention are characte-
rized by a high hardnes~ and an excellent impact strength at a
temperature below O C.
The polymerization is carried out continuously or discon-
tinuously in suspension or in the gaseous phase at a pressure
; 10 of from 1 to 50 kg/cm2~ preferably 1 to 40 kglcm .
~ The suspen~ion polymerization is carried out in an inert
solvent, for example a petroleum fraction poor in olefins and
having a boiling point in the range of from 60 to 250 C which
must be carefully freed from oxygen, sulfur compounds and humi-

dity, or saturated aliphatic and cycloaliphatic hydrocarbonssuch as butane, pentane~ hexane~ heptane, cyclohexane, methyl-
cyclohexane, or aromatic compounds such as benzene~ toluene,
and xylene. The suspension polymerization can advantageously
be carrled out also in the O~-olefin to be polymerized, for ex-

ample liquid propylene, as dispersion medium.
It is likewi~e possible to carry out the polymerizationin the absence of a solvent in the gaseous phase, for exa~ple
in a fluidized bed.
If neces~ary, the molecular weight of the polymer i9 re-

gulated by addi~g hydroge~.
The amount of catalyst component A depend~ on the intend-
ed reaction conditions, especially temperature and pressure.
In general, 0.05 to lO m~oles of TiCl3 and preferably O.1 to 3
; mmoles, are used per liter of Aolvant in the suspension poly-


_ 9 _

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., .. . . . ' .. : . :

HOE 74/F o64 K
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merization or per liter of reactor volume in the gas phase
polymerization.
Catalyst component B is an aluminum dialkyl monochloride
the formula Al~2Cl in which R is an aliphatic hydrocarbon
radical having up to 8 carbon atoms, preferably aluminum di-
ethyl monochloride. The amount of component B is chosen in
. , .
such a manner that the molar proportion of component B to com-
ponent A (calculated on TiCl3) is in the range of from 0.5 to
1 to 100 : 1, preferably 1 s 1 to 10 : 1. -
~- 10 The catalyst consisting of components A and B has a high
polymerization activity and a good stereospecificity which lar-
~ gely depends on the polymerization temperature. When, for ex-
- ample, propylene is polymerized at 60 C the di~persion medium
`i contains less than 3.0 ~ by weight of soluble fractions, cal-
culated on the total polymer, preferably less than Z.O ~ by
weight. At a ~lymerization temperature of 70 to 80 C the un-

~, desired soluble fraction increase~ to up to 6 ~ by weight. On
i the other hand, a higher polymerization temperature i9 deQir-
able with respect to the dissipation of the polymerization
ZO heat.
i It i~ known that with increasing pressure and~ hence, at
.; ~
~ a higher polymerization rate, the amount of soluble fractions
"
., .
increasec. When, for example, propylene i8 polymerized in

liquid propylene under about 32 kg/cm2 and at 70 C, up to 6
;J
of soluble fractions are obtained.
The good stereospecificity of the two component catalyst
at higher polymerization pre~sure and temperature can be fur-


~ ther improved by using a cyclopolyene as catalyst component C,
- such as specified above. Component C i9 aclded to component A
. .

-- 10 --
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HOE 7~ F o64 K
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~uitably together with component B at the beginning of polyme-
rization. The molar proportion of component C to component A,
calculated ~s TiC13, is in the range of from 0.1 : 1 to 1 : 1,
preferably 0.2 : 1 to o.6 : 1.
Th~ polymerization in the presence o f the catalyst of the
invention is carried out at a temperature of from 20 to 120 C,
preferably 50 to 90 C. Higher temperatures are also possible
but in this case a higher fraction of soluble atactic polymer
- i 9 formed.
By the after-treatment according to the invention with an
aluminum alkyl halide of the TiC13-containing reaction product
thermally treated in the presence of a cheap aliphatic dialkyl
ether a catalyst component (A) is obtained which, already in
combination with an aluminum dialkyl halide a~ activator ~com-
ponent B)~ considerably increase~ the polymerization rate of
O~-olefin~ with improved stereospecificity. As compared to the
state of the art as disclosed in 9ritish Specification 895,595,
the catalyst acti~ity is over 100 ~ higher at the same polyme-
rization temperature and pre~sure with an improved 6tereospeci-
ficity. Owing to the higher catalyst activity (g polymer per
g catalyst) the same space-time-yield can be abtained with a
smaller amount of catalyst, whereby the expensive further pro-
ce~ing of the polymer is considerably facilitated or a pro-
.
cessing under like conditions ensures a more efficient removal
of the cataly~t. When the polymerization is carried out under
elevated pressure, for example above 20 kg/cm , either in the
gaseous phase or in liquid ~-olefin, for example liquid propy-
lene, the yields obtained are ~o high that a cataly~t removal
can be dispensed with (more than 1,000 g polymer per millimole
.~. ' . i
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-- 1 1 --

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HOE 74/F o64 K
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- 1063588
TiC13) .
As compared with the state of the art disclosed ln Ger-
man Offenlegungsschrift 2,213,086 the advantage of the process
of this invention resides in the fact that the manufacture of
the catalyst is cheaper for the following reasons:
1) At least one and possibly even two of the three in-
ten~e washing processes can be dispensed with.
2) Lower investment and manufacturing costs for the
working up of wash solutions.
3) Economy of material since the after-treatment accord-
ing to the invention can be carried out with the mother liquor
obtained in the preparation of the reduced TiC13-containing
solid~ or, when an aluminum dialkyl monohalide is u~ed, the
amount thereof can be decuded from the amount of activator
(component B).
4) According to-the state of the art the titanium tetra-
chloride used for the after-treatment i~ decomposed with water
and neutralized whereby considerable amounts of waste water are
formed, whereas practically no titanium-containin~ waste waters
must be worked up in the manufacture of the catalyst according
~ to the invention.
`s~ The following examples illustrate the invention.
- E x a m p 1 e s 1 - 14
A) Preparation of catalyst
A 1) Reduction of TiCl4 with aluminum ethyl sesqui-
chloride
With the exclusion of air and moisture a lO llter vessel
with stlrr~r wa~ ~harged wlth 1.090 ml of a hydrogonated, oxy-
gen-fr~e gasoline fraction boiling at 140 - 165 C and 550 ml
:'

- 12 -

_ . _ _ _ _ _ _ _ _ ., , ... _ . _ _ ... . _ _ .. _ .. _ .... . _ .. ..... .. .. . .. .. . .... _ _ . .... . . .... . _ . _
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.
'

HOE 74/F o64 K
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of titanium tetrachloride (5 moles) and at 0 C, while stirring
under nitrogen (250 rev/min), a solution of 1111.2 g of alumi-
num ethyl ~esquichloride containing 4.5 moles aluminum diethyl
monochloride in 3334 g of the gasoline fraction was dropped in
over a period of 8 hours. A red-brown fine precipitate sepa-
rated. The mixture was stirred for another 2 hours at 0 C
and then for 12 hours at room temperature.
The separated precipitate was allowed to settle and the
supernatant mother liquor was separated by decantation and
washed three times, each time with 2,000 ml of the gasoline
; fraction. The washed solid reaction product w~ suspended
again in the ga~oline fraction and the concentration of the
suspension was adjusted to 2 moles TiCl3/liter. The content
of trivalent titanium in the suspension was determined by
jl
titration with a Ce-IV solution.
A 2) Thermal treatment of the TiCl3-contalning reaction
product in the presence of di-n-butyl ether
; 500 ml of the 2-molar suspension (corresponding to 1 mole
TiCl3) were heated to 85 C in a 2 liter vessel with stirrer,
with the exclusion of air and humidity and under nitrogen and
at said temperature 161 ml di-n-butyl ether (0.95 mole) were
dropped in while stirring over a period of 30 minutes. The
suspension wa~ kept at 85 C for one hour. On adding the ether
the mother liquor turned olive green.
A 3) After-treatment of the TiCl3-containing reaction
product with aluminum alkyl halides
Each time 100 mmoles (TiCl3) of the above olive green
suspension were treated with an aluminum alkyl halide a~ ~peci-
fled in the following Table 1. The treatment was carried out

- 13 -
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HOE 74/F 064 K
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at 35C while stirring under nitrogen or argon. After the
addition of the aluminum alkyl halide, stirrirg was continued
for a further hour at 35C. Component A, either washed (3 to
5 times with the gasoline fraction) or not, was used for the
polymerization in the form of a suspension. The TiC13 content
- of the suspension was determined and for polymerization 1 mmole
TiC13 was used.
B) Polymerization of propylene
A 1 liter glass autoclave was charged, with the exclusion
of air and humidity, with 0.5 liter of a hydrogenated, oxygen-
free gasoline fraction (b.p. 140 - 165C) and the gasoline
was saturated with propylene at 55C. There were added the
amounts of Al(C2H5)2Cl (activator, component B) indicated in
the following Table 2 and then component A, prepared as des-
cribed above (cf. Table 1) in an amount corresponding to 1 mmole
TiC13. 0.25 kg/cm hydrogen was forced in and over a period of
5 minutes propylene was introduced in an amount such that a
pressure of 6 kg/cm2 was obtained. During the course of poly-
merization this pressure was maintained by adding propylene.
After a time of polymerization of 2 hours the pressure in the
autoclave was released and the polymer suspension was filtered
off with suction, the polymer on the filter was washed with
1 liter of hot solvent (70C) and dried at 70C under reduced
pressure.
To determine the soluble fraction formed in the polymeri-
zation (atactic polypropylene) the mother liquor of the polymer
suspension and the wash solutions were combined and evaporated
to dryness under reduced pressure. The polymerization results
are listed in the following Table 2.
- 14 -

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HOE 74/F o64 K
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E x a m p 1 e 15
A) Preparation of catalvst
100 mmole~ TiC14 were reduced under the conditions of Ex- ;
ample 1, A l). After settllng of the reaction product, the
supernatant mother liquor was separated and set aside. The
solid reaction product was washed and subjected to a thermal
treatment in 2 molar concentration wlth 95 mmoles di-n-butyl
ether as indicated in Example 1, A 2). The after-treatment of
the suspension was effected with the separated mother liquor
) 10 containing aluminum ethyl dichloride obtained after the reduc-
tion of TiC14. The mother liquor was added to the suspension
at 35 C while ~tirring over a period ~f 10 minutes and stir-
~, ring was continued for an hour at 35 C. Catalyst component A
was washed three times with an inert solvent.
B) Polymerization of propylene
The polymerization was carried out a~ indicated in Ex-
ample 1 B) using the abo~e catalyst component A (1 mmole TiCl3).
After a polymerization period of 2 hours 140 g of insoluble
crystalline polypropylene having an apparent density of 460 g/l
and an RSV value of 3.8 dl/g were obtained. The polymerization
medium contained 2.79 g of soluble polypropylene, correspond-
ing to 1.9 ~ by weight.
E x a m ~ 1 e 16
Polymerization of propylene
A 150 1 enamelled vessel, heated to 60 C and provided
with stirrer, jacket heating and gas inlet, was charged, with
the careful exclusion of atmospheric oxygen and humidity, with
70 l of a hydrogenated, oxygen-free gasoline fraction (b.p.
140 - 165 c), the hydrocarbon was saturated with propylene

. '
, - 15 -
-


. '


:
' .

,~ ~IOE 74/F o64 K
~--`` 1063588
and under nitrogen a solution of 67 g of aluminum diethyl mono-
chloride (560 mmoles, component B) in 203 g of the gasoline
fraction was added.
After stirring for 10 minutes 70 mmoles (TiCl3) of the
suspension of Example 8 were added. Polymerization started
., .~
after a few minutes. After a rapid pressure increase to 1.5
kg/cm2 within 15 minutes by the introduction of propylene, the
pressure was kept constant by introducing the necessary amount
of propylene containing 0.15 ~ by volume o~ hydrogen. The poly-
merization temperature was maintained at 60 C by cooling.
After a period of 12 hour~ the polymerization was interrupted
by adding 1.4 l of isopropanol, the reaction mixture was stir-
red for 2 ho~rs ~t 60 C, tre,ated three times, each time with
30 l of water for 30 minutes and the aqueous layer was separat-
ed. After filtration, the solid was sub~ected to a steam di-
stillation for 12 hours with the addition of 0.05 ~ by weight
of an emulsifier (ethoxylated stearic acid). After isolation
from the aqueous phase and drying under reduced pressure, 30 kg
of colorless pulverulent polypropylene were obtained having an
RSV value of 3.4 dl/g, and an apparent density of 508 g/l and a
ball indentation hardness of 820 kg/cm . 430 g of polypropy-
lene were obtained per mole TiCl3.
The soluble fractlon in the mother liquor was determined
by evaporating a sample under reduced'pressure. It amounted to
1.8 ~ by weight, calculated on the total polymer.
E x a m p l e 17
, ' ,
Preparation of a propylene copolymer with statistically
, incorporated ethylene
: Thc polymerization was carried out as described in Ex-
~ ~ .
_ 16 -

. . , : .

- .
':
- . , ~ : :
: ~: : ' ~ ' . :' ' .

- HOE 74/F o64 K
-~ 1063588
ample 16. The introduced mixture of propylene with 0.1 ~ by
volume Or hydrogen was admixed with 4.5 ~ by volume of ethylene.
After working up under the conditions of Example 16, 28.7 kg of
copolymer were obtained having an RSV value of 3.0 dl/g~ an ap-
parent density of 470 g/l and a ball indentation hardness of
590 kg/cm2. The content of ethylene, determined by IR spectro-

~- scopy was found to be 2.8 ~ by weight.
;` The content of soluble fraction in the mother liquor was
~l'3
3.1 ~ by wei~ht, calculated on the total copolymer.

Shaped articles and sheets of very good transparency

could be made from the copolymer obtained.

E x a m p l e 18

Sequence copolymerization of propylene and ethylene

Under the condition~ of Example 16 the 150 liter vessel
: ~ .
was charged with 100 l of the hydrogenated, oxygen-free
gasoline fraction. First 67 g of aluminum diethyl monochloride
(560 mmoles) and then 200 mmole~ (TiCl3) of the suspension ac-
- cording to Example 8 were added.
At a polymerization temperature of 55 C propylene having
ZO a hydrogen content of 0.38 ~ by volume was introduced i`or
5 hours in an amount of 5.5 kg/hr. After having stopped the
supply of gaseous monomer, the propylene pressure in the vessel
was allowed to drop to 1.7 kg/cm2, for which about 30 minutes

. , .

were required. A current of 3.25 kg/hr of gaseous ethylene wa~
~::
then introduced for 50 minutes.

The polymerizatlon w~ interrupted by adding 1.4 l lso-

pr<>p~rlol ~nd th~ mlxt~lre we~ work~-l u~ under tl1o ~ondltiol1~ of

~xample 16. After drying 28.3 k~ of a polymer mixture were ob-

- tained which preponderantly consisted of polypropylene and a


- 17 -

".:, ,,, , :.
,: . . , -
.,.. , -: .,, . . - , . . , . ... - . : :

HOE 74/F o64 K
j; --` 1063,~i,88
propylene-ethylene copolymer with randomly distributed monomers
(RSV 2.8 dl/g, apparent density 485 g/l, ball indentation hard-

- ness 66 kgtcm2, notched impact strength 24.3 kgcm/cm2 at +23 C,
15.2 ~gcm/cm2 at 0 C and 9.9 kgcm/cm2 at -20 C). The ethylene
content determined by IR spectroscopy was found to be 8.1 '~.
The mother liquor contained 3.6 ~ by weight of ~,oluble
polymer calculated on the amount of gases used.
~; E x a m p 1 e 19
Polymerization of propylene in liquid monomer
A 16 liter enamelled vessel provided with stirrer, jacket
heating and gas inlet was flushed at room temperature with pure
nitrogen and then with propylene. A pressure of 0.5 kg/cm2 of
hydrogen was built up and through a valve a solution of 32
mmoles Al(C2H5)2Cl in 6 ]iter of liquid propylene and a suspen-
8ion ~ mmoles TiC13) ofthe isolated catalyst component A, ac-
cording to Example 8, Table 1, in 6 liters of liquid propylene
' were added. The vessel was heated to 70 C whereby the pressure
rose to about 32 kg/cm . The internal temperature was main-
tained at 70 C by cooling. Polymerization started after a
2() few llinutes and was interrupted after 6 hours by r~e~leasing the
' monomer which had not polymerized. After drying 5.2 kg of a
freely flowing polymer having an apparent density of 530 g/l
;
were obtained. The reduced specific viscosity (RSV) was 2.9

dl/g. By a 16 hour extraction with heptane a soluble fraction

of 7.8 ~ by weight was found. The ball indentation hardness

wn~ 630 k~/cm .


~, I'; X e m 1) 1 e 20
' 1 ' ' . .
Polymerizatlon of propylene in the gaseous phase

~! A horizontal reactor wlth stirrer scraping along the in-
-
- 18 -
,:




,: . . ~ , , :, , : . . .:

HOE 74/F o64 K
-~ 1063588
ternal wall was charged with 1.5 kg polypropylene, the reactor
was flushed by repeatedly forcing in propylene with subsequent
pressure release and heated to 70 C. A solution of 7.74 g
Al(C2H5)2Cl (64 mmoles) in 23.1 g of a gasoline fraction (b.p.
140 - 165 C) anf 8 mmoles (calculated as TiC13) of the suspen-
ffion prepared according to Example 8, Table 1, were added.
1.5 kg/hr propylene were then introduced and the temperature
was maintained at 70 C. The pressure rose, rapidly at the
beginning but more slowly later on. The polymerization was in-
terrupted at a pressure of 20 kg/cm2 (after about 9 hours).
After pressure release, 12 kg of colorless polypropylene were
obtained without further purification.
. . .
By extraction with heptane 8 ~ by weight of soluble poly-
propylene were obtained.
E x a m n 1 e 21
~ Polymerization of 4-methylpentene-1
i A 2 liter vessel with stirrer, thermometer and gas inlet
.... .
was charged, with the exclusion of air and humidity, with 1 1
of hydrogenated, oxygen-free gasoline fractlon (b.p. 140 -
165 C) and scavenged with pure nitrogen. At 50 C, 8 mmoles
of aluminum diethyl monochloride (0.97 ml) and 5 mmoles (calcu-
lated on TiC13) of the suspension prepared according to Ex-
ample 8, Table 1, were added. During the course of 3 hours
200 g of 4-methylpentene-1 were added dropwise. The polymeri-
zation temperature was maintained at 55 C. Polymerization
started after a few mlnutes and the polymer separated in the
form of a fine precipitate. When the dropwise addition was
terminated the polymerization mixture wa~ ~tirred for another
, 1 .
i~ 2 hours at 55 C and the polymerizatlon was interrupted by add-

~ 19 -

HOE 74/F o64 K
~- 1063~88
ing 5~ ml of isopropanol, the mixture was stirred for 1 hour
at 60 C, extracted with warm water and filtered with suction
while still hot. After thorough washing with hot solvent
(gasoline) and acetone and drying under reduced pressure at
70 C, 193 g of colorless poly-4-methylpentene-1 were obtained
ha~ing an apparent density of 500 g/l. The mother liquor was
found to contain 0.5 % by weight of soluble fraction.
E x a m p l e s 22_- 29
A) Preparation of catalyst
A 1) and A 2) A TiCl3-containing ~uspension was prepar-
ed as described in Example 1.
A 3) After-treatment with an aluminum alkyl halide
With the exclusion of air and humidity 200 mmoles alumi-
; num diethyl monochloride ( 25 r 16 ml) were added at 35 c over a
period of 2 minute~ to 100 ml (200 mmoles TiCl3) of the olive
green ~uspension and the mixture was stirred for 1 hour at
35 C. The catalyst component was used for polymerization
withollt being washed. The content of the suspension of tri-
. j .
valent titanium was determined by titration with a Ce-IV
solution (as TiCl3).
B) Polymerization of propylene
- A 1 liter glass autoclave was charged, with the exclu-
sion of air and humidity, with 0.5 l of a hydrogenated gaso-
line fraction (b.p. 140 - 165 C) and saturated with propylene
at 55 C. The amounts of Al(C2H5)2Cl (activator, component B),
freshly distilled cycloheptatriene-1,3,5 (component C) in the
form of a 1-molar solution in the gasoline frAction and th~n
catalyst component A (oach time 1 mmole TiCl3) indicated in
Table 3 were then added, 0.25 kg/cm of hydrogen was forcod

- 20 -

.... ~:



: . . : : . ;~ . .. ~ :. - . . -
- . :
:: ~ : ::: . . .
: ~
., : . :.

- HOE 74/F o64 K
~' 1063~88
in and within 5 minutes propylene was introduced in an amount
to build up a total pressure of 6 kg/cm . This pressure was
maintained during the course of polymerization by adding propy-
- lene. After a time of polymerization of 2 hours the pressure
in the autoclave was released and the polymer suspension was
filtered off with suction, the polymer was washed on the filter
with 1 1 of hot solvent (7~o c) and dried under reduced pressure
at 70 C.
At a polymerization temperature above 60 C (cf. Table 3~
the mixture was first polymerized for 10 minutes at 60 C where-
- upon the temperature was raised to the higher level.
E x a m p 1 e 30
Polymerization of propylene in liquid monomer
A 16 1 enamelled vessel provided with stirrer~ jacket
heating and gas inlet was flushed at room temperature with pure
nitrogen and then with propylene. A pressure of 0.5 kg/cm of
hydrogen was built up and through a valve a solution of
32 mmole~ Al(C2H5)2Cl in 6 1 of liquid propylene, a suspension
of the catalyst component A of Example 1 (Table 1) (4 mmoles
TiC13) and 2.4 ml of a 1-molar solution of cycloheptatriene-
1,3,5 (component C) in hexane (2.4 mmoles) and finally 6 1 of
liquid propylene were added. The polymerization mixture was
heated to 70 C whereby the pressure rose to about 32 kg/cm .
, The internal temperature was maintained at 70 C by cooling.
i Z5 The polymerization started after a few minutes. The experiment
was interrupted after 6 hours by releasing the pressure. After
drying 4.9 k~ of a freely flowing polymer having an apparent
density of 540 g/l and an RSV value of 2.5 dl/g were obtained.
By 16 hour extraction with heptane a soluble fraction of 4.8

~: `

: ;

- .:: ~
. :
,: . -- - .
-:
-:: : : '
. : :- - : . . :: :
- . . : . . -
:, . .
.
'.:

HOE 74/F o64 K
1063~88
by weight was found. The ball indentation hardness of the poly-
- mer was 750 kg/cm (DIN 53 456)-
~ len the polymerization was carried out under identical
conditions but with a catalyst which did not contain component
C, the polypropylene contained a soluble fraction of 7.8 ~ (cf.
Example 19).
E x a m p l e 31
A) Preparation of catalyst
A 1) Reduction of TiCl4 with aluminum ethyl sesqui-

10chloride
A 10 liter vessel with stirrer was charged, with the ex-
clusion of air and humidity,with 1090 ml of a hydrogenated,
oxygen-free gasoline fraction (b.p. 140 - 165 C) and 550 ml
titanium tetrachloride (5 moles) and at 0 C a solution of
1511t1.2 g of aluminum sesquichloride (containing 4.5 moles alu-
minum diethyl monochloride) in 3334 g of the gasoline fraction
were added dropwise while stirring (250 rev/min) over a period
Or 8 hours under nitrogen. A red-brown fine precipitate sepa-
rated. The mixture was stirred for 2 hours at O C and for
12 hours at room temperature.
After settllng of the precipitate, the supernatant mother
liquor was decanted and the solid reaction product was washed
three timeq, each time with 2000 ml of the gasoline fraction.
For further processing it was suspended in the gasoline frac-

tion in such an amount that the concentratlon was 2 molesTiCl3/l. The content of trivalent titanium in the suspension
was determined by titration with a Ce-IV solution.
A 2) Thermal traatment of the TiCl3-containing reaction
product in the presence of di-n-butyl ether



- 22 -



:. ~ . ' ,: - . ,. , ,',: ~ , . . ~.:
'. ' ' ' ' ' . . ~ , '

- HOE 74/F o64 K
1063~i88
In a 2 liter ~essel with stirrer 500 ml of the 2-molar
suspension (corresponding to 1 mole TiCl3) were heated to 80 C,
with the exclusion of air and humidity, and under nitrogen and
at said temperature 161 ml di-n-butyl ether (0.95 mole) were
added dropwise while stirring within 30 minutes. The suspen-
sion was then maintained for 5 hours at 80 C. On adding the
ether the mother liquor turned olive green. For the further
treatment the suspension was diluted to a TiCl3 content of
0.5 mole/l. The content of trivalent titanium (as TiCl3) was
determined by titration with a Ce-I~ solution.
A 3) After-treatment of the TiCl3-containing reaction
product with aluminum alkyl halides and a cyclo-
- polyene
With the exclusion of air and humidity 1 mmole (TiC13)
of the above olive green suspension, 0.2 mmole cyclohepta-
triene-1,3,5 and 2 mmoles aluminum diethyl monochloride were
added to 100 ml of the gasoline fraction and the mixture was
stirred for 1 hour at room temperature.
B) Polymerization of propylene
A 1 liter glass autoclave was charged, with the exclusion
of air and humidity, with 0.4 l of a hydrogenated, oxygen-free
gasoline fraction (b.p. 140 - 165 C) and the hydrocarbon was
saturated with propylene at 55 C. 2 mmoles aluminum diethyl
monochloride (activator, component B) and then the after-
treated TiCl3 suspension obtained according to A 3) (1 mmole)
were added. Hydrogen was introduced until a pressure of 0.25
kg/cm had been reached and during the course of 5 mlnutes pro-
pylene wa.s introdllced to build up a total press~re o r 6 kg/cn) .
r~ r~ Wi~R mi~lrl~ n(~3 r~lJr~lr~ C~(J~ .,r l)Oly,n." 1,.~-

- 23 -



. :

I~OE 74/F o64 K
,, --
; 1063588
tion by adding propylene. After a time of polymerization of
2 hours the pressure in the autoclave was released and the poly-
mer suspension was filtered off with suction. The filter cake
was washed with 1 liter of hot solvent (70 C) and dried under
reduced pressure at 70 C. 237 g of polypropylene inAoluble in
the dispersion mediuM were obtained. The apparent density of
the freely flowing pulverulent polymer was 524 g/l, the RSV
value was 2.8 dl/g and the ball indentation hardness 800 kg/cm
(DIN 53 456). To determine the soluble fraction (atactic poly-

mer) formed the polymerization mother liquor and the wash solu-
tions were combined and evaporated to dryness under reduced
pressure. 1.5 g of soluble polypropylene were found (0.62 ~,
calculated on total polymer).

:
E x a m p l e 32
Component A was prepared a~ described in Example 31 with
the exception that cyclooctatetraene-1,3,5,7 was used instead
of cycloheptatriene-1,3,5. With the exclusion of air and humi-
dity 1 mmole (TiCl3) of the olive green suspen~ion of Example
31, A 2), 0.2 mmole of cyclooctatetraene-1,3,5,7 and 2 mmoles
aluminum diethyl monochloride were added to 100 ml of the gaso-
llne fraction and the mixture was stirred for 1 hour at room
temperature.
Propylene was polymerized under the conditions of Ex-
ample 31. 242 g of polypropylene insoluble in the dispersion
med~um and having an apparent density of 510 g/l, an RSV value
of 3.0 dl/g and a ball indentation hardness of 820 kg/cm (DI~
53 456) wer~ obtained. The fraction of soluble polypropylene
amounted to 1.3 g - 0.53 %, calculated on the total polymer.

E x a m p l e ~3


_ 24 -

.



- .
. .
. - . :, . . ~, :

HOE 74/F o64 K
~- 1063588

Component A was prepared as described in Example 31. The
after-treatment of the TiCl3-containing reaction product (A 2)
with the aluminum alkyl halide and a cyclopolyene was carried
out in the presence of an olefin as follows:
10~ mmoles of the TlCl3 suspenAion A 2) were diluted to
- 0.1 mole TiCl3 per liter dispersion medium by adding about
800 ml of the gasoline fraction and, with the exclusion of air
and humidity, 500 mmoles Al ~C2H5)2Cl (62.92 ml) and 40 mmoles
c~cloheptatriene-1,3,5 (4.16 ml) were added and then the mix-
ture was stirred for 5 minutes at room temperature. At room
~` temperature (with cooling) 300 mmoles (12.6 g) of gaseous pro-
pylene (6.7 l) were then introduced over a period of 1 hour.
To a~oid the formation of a vacuum the propylene was diluted
with a small amount of argon. Subsequently9 the TiCl3-contain-
ing suspension was stirred for 1 hour at room temperature and
under argon. The content of trivalent titanium (as TiCl3) was
determined by titration with a Ce-IV solution.
A 1 liter glass autoclave was charged, with the exclu-
sion of air and humidity, with 0.5 l of a hydrogenated, oxygen-
free gasoline fraction (b.p. 140 - 165 C) and the hydrocarbon
was saturated with propylene at 70 C. 1 mmole of the above
suspension (10.9 ml) was added and hydrogen was introduced in
an amount such that a pressure of 0.25 kg/cm was reached.
Over a period of 5 minutes propylene was then introduced until
a total pressure of 6 kg/cm2 had built up. This pressure was
maintained during the course of polymerization by introducing
- propylene. Simultaneously, the temperature wa~s increased to
80 C and maintained at said level by cooling. ~ft~r a po~y-
merization period of 2 hour.s the pressure in the autoclave was

- 25 -



.-
,. - .

.

HOE 74/F o64 K
~` 1063588
released and the polymerization mixture was worked up as des-
cribed in ~xample 31. 220 g of polypropylene insoluble in the
disper~io~ medium were obtained in the form of tran~lucent
grains. Th- n8v value was 2.0 dl/g, the apparent dens:ity 5~5
g/l and the ball inderltation hardness ~50 kg/cm (DIN 53 456~.
IJI the mother li~uor 4.5 grams of soluble atactic polypropylene
were found~ corresponding to 2.0 ~ by weight, calculated on the
total polymer.
E x a m p l e 34
Polymerlzation of propylene in the liquid monomer
A 16 l enamelled vessel provided with stirrer, jacket
heating and gas ihlet was flushed at room temperature with pure
nitrogen and then with propylene. A pressure of 0.5 kg/cm was
built up by introducing hydrogen and through a valve a solution
; 15 of 20 mmoles Al (C2H5)2Cl in 6 l of llquid propylene were added.
Then through another valve 4 mmoles (as TiCl3) of the suspen-
sion of component A of Example 33, containing 20 mmoleq
Al(C2H5)2Cl, 1.6 mmoles cycloheptatriene-1,3,5 and a small
amount of polypropylene, diluted with 6 l of liquid propylene
were added. The polymerization mixture was heated to 70 C
whereby the pressuro rose to 32 kg/cm . The internal tempera-
ture was maintained at 70 C by cooling. The polymerization
started after a few minutes. The experiment was interrupted
after 3 hours by pressure release. After drying, 3.8 kg of a
freely flowing polymer were obtained having an apparent densi-
ty of 550 g/l. The polymer grains were translucent, the XSV
value was found to be 2.1 dl/g. By a 16 hour extraction with
heptane a soluble fraction of 3.0 ~ by weight was found. The
product had a ball indentation hardness of 780 kgjcm2 (DIN

- 26 _


.. ,, , . : : : . , .: :
.. . . ~
: . :

: ~, ~ . ', -. ' :

- ' ' ' ". ' ~ ' '

HOE 74/F o64 K
:10635~8
53 456).
E x a m p 1 e '3 5
5 mmolss (TiC13) of the olive green suspension according
to ~xample 31 were suspended~ with the exclusion of air and hu-

midity, in 500 ml o~ the gasoline fraction and 10 mmoles alumi-
num diethyl monochloride and 1 mmole cycloheptatriene-1,3,5
;~ were added. The reaction mixture was then stirred for 1 hour
at room temperature.
; A 2 1 vessel with stirrer~ thermometer and gas inlet was
charged with 1 1 of the hydrogenated, oxygen-free gasoline
fraction (b.p. 140 - 165 C) and flushed with pure nitrogen.
At a temperature of 50 C the suspension described above was
added and 200 g of 4-methylpentene-1 were dropped in over a
period of 3 hour~. The polymerization temperature was main-
tained at 55 C. The polymerization set in after a few minutes.
The polymer separated in the form of a fine precipitate. When
the dropwise addition was terminated the mixture was stirred
for another 2 hours at 55 C. Thereafter, the polymerization
was interrupted by adding 50 ml isopropanol, the mixture was
stirred for 1 hour at 60 C, extracted with warm water and fil-
tered off with suction while still hot. After thorough washing
with hot gasoline and acetone and drying under reduced pressure
at 70 C, 196 g of colorless poly-4-methylpentene-1 were ob-
tained. The polymer had an apparent density of 520 g/l. The
; 25 mother liquor contained 0.4 ~ by weight of soluble polymel.


:~
.`

- 27 -

.


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HOE 74/F' o64 K

1063588

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