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Патент USA US3046274

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Staes atent O?tice
Patented July 24, 1962
preferably 3 to 7 carbon atoms can be polymerized by the
present process.
Watchung, N.J., assignors to Esso Research and En
gineering Company, a corporation of Delaware
The catalysts employed herein are activated, partially
reduced heavy transition metal compounds or activated,
partially reduced heavy transition metal compounds co~
Erik Tornqvist, West?eld, and Arthur W. Langer, In,
No Drawing. Filed Apr. l, 1953, Ser. No. 725,507
2 Claims. (Cl. 260-933)
crystallized with a group II or III metal compound. The
group II or III metal compound is preferably a halide
such as aluminum chloride, zinc chloride and the like.
This invention relates to ‘a process for preparing poly
mers of propylene or higher ‘alpha ole?ns. More par 10 The partially reduced heavy transition metal compounds
include inorganic compounds, such as the halides, oxy
ticularly, this invention relates to the low pressure prepa
halides, complex ‘halides, oxides, and hydroxides, and
ration of polymers of propylene or higher alpha ole?ns
organic compounds, such as alcoholates, acetates, benzo
using a preformed crystalline catalyst.
ates, and acetonates of the transition metals of the IV,
This application is ‘a continuation-in-part of US. Serial
V, VI, and VIII groups of the periodic system e.g. ti
No. 578,198, ?led April 16, 1956.
tanium, zirconium, hafnium, thorium, uranium, vanadium,
The low pressure polymerization of alpha ole?ns with
niobium, tantalum, chromium, molybdenum, tungsten and
catalyst systems made up of reducible heavy transition
iron. The metal halides, particularly the chlorides, are
metal compounds and a reducing metal-containing com
pound to high density, isotactic, relatively linear prod
generally preferred; especially purple crystalline titanium
ucts has been assuming ever increasing importance and 20 trichloride. Purple crystalline titanium trichloride co
crystallized with aluminum chloride is particularly pref
is now well known, see e.g. Belgian Patent 533,362,
erred. When the catalyst is a partially reduced heavy
“Chemical and Engineering News,” April 8, 1957, pages
transition metal compound cocrystallized with a group II
12 through 16 and “Petroleum Re?ner,” December 1956,
or III metal compound, the catalyst contains from 0.05 to
pages 191 through 196.
It was found prior to this invention that the polymeri 25 10, preferably 0.1 to 0.5 mole of the group II or III
metal compound per mole of partially reduced transition
zation of propylene or a higher alpha ole?n is most effec
metal compound.
tively carried out with aliphatic diluents when using a
The partially reduced heavy transition metal com
catalyst system made up of a reducible heavy transition
pounds can be prepared by any procedure known to the
metal compound such as TiCl4 and a reducing metal-con
taining compound, such as an alkyl aluminum compound. 30 art and the preparation of these compounds is not within
the scope of the invention. However, some of the meth
When aromatic diluents such as xylene were used in the
ods known for preparing the preferred catalysts of the
polymerization reaction and/or the catalyst preparation,
invention, i.e. purple crystalline titanium trichloride and
low yields of polyole?ns were obtained. It was also dis
purple crystalline titanium trichloride co-crystallized with
covered, prior to the present invention, that propylene or
a higher alpha ole?n can be polymerized at substantially 35 aluminum chloride are summarized below.
atmospheric pressure using this catalyst system in an ali
(1) Reduction of titanium tetrachloride with aluminum
phatic diluent. However, no method of polymerizing pro
powder in xylene at 100—175° C. at atmospheric pres
pylene or a higher alpha ole?n at substantially atmospheric
pressure at high polymerization rates using a preformed
catalyst system made up of an activated, preformed, crys~ 40 (2) Metal reduction of titanium tetrachloride with alu
minum powder, titanium powder, or mixtures of alu
talline, partially reduced heavy transition metal com
minum and titanium powder in the absence of solvent
pound such as AlEtg-activated TiCl3 was known. This
at elevated temperatures. ,
preformed catalyst system is desirable for obtaining steri
cally oriented polymers of ole?ns having more than 2
(3) Hydrogen reduction of titanium tetrachloride at tem
peratures above about 650° C.
carbon atoms.
4.5 (4) Reduction of titanium tetrachloride with metal alkyls,
It has now been discovered that substantially atmos
AlEt3 in particular, in an inert diluent above about
pheric polymerization of propylene or higher alpha ole- .
130° C.
?ns can take place with an activated preformed catalyst
Heating a mixture of titanium tetrachloride and an
system when the reaction is carried out in an aromatic
diluent under carefully controlled conditions to produce 50
superior polymers.
As an example of these superior polymers, the poly
propylene prepared by the present process is ‘believed to
have physical properties superior to any polypropylene
aluminum alkyl after the formation of a brown precipi
tate at a temperature above about 70° C. in the pres
ence of an inert diluent.
(6) Reducing titanium tetrachloride with an aluminum
trialkyl by carrying out the reduction in temperature
graded stages in an inert diluent and with aluminum
known to the art. In particular, the polypropylene of 55
trialkyl/TiCl, mole ratio of about 0.33/1.
the invention is less than 15% soluble in n-heptane and
(7) Heat decomposition of TiClqc at above about 1000° C.
has a tensile strength of over about 5000 psi. Modi?ca
tions of the present process have given polypropylene
The above catalysts of the invention are activated with
with a solubility in n-heptane of about 10% and a tensile
organo-metallic compounds, preferably organo-aluminum
strength of about 6000 psi. Accordingly, it can be seen 60 compounds, and especially aluminum alkyl compounds,
that this polypropylene is highly crystalline.
such as alkyl ‘aluminum halides and trialkyl aluminum,
The alpha ole?ns useful in the present process include
e.g. triethyl aluminum. Other organo-metallic com
propylene and higher alpha ole?ns such as butane-1, hep
pounds that can be used include dialkyl zinc, dialkyl mag
tene-l, dodecene-l and the like, with propylene preferred.
nesium, triaryl aluminum, ‘and complexes such as lithium
In general, alpha ole?ns having at least 3 carbon atoms, 65 aluminum
tetraalkyl. In general, from 0.1 to 5.0 moles
- 3,646,264
of the ‘activating organo-metallic compound per mole or
partially reduced transition metal halide is added to the
reaction was completed, 500 cc. of isopropyl alcohol was
added to the stirred mixture to decompose the catalyst
catalyst in an aromatic diluent.
The polymerization of propylene or a higher alpha
ole?n is carried out by diluting the activated catalyst
solution with ‘additional aromatic diluent, preferably to
stirred at 70° C. for ‘10 minutes, the solid polymer was
?ltered off at ‘50° C., washed with 500 cc. of hot isopropyl
alcohol, and dried in vacuum. The catalyst preparation,
obtain a catalyst concentration of about 0.1 to 0.5 wt.
percent based on the weight of diluent and then saturat
the polypropylene obtained are given in Table ‘I.
and precipitate the polymer, the resulting mixture was
polymerization reaction conditions and the properties of
ing the resulting dispersion with the alpha ole?n to be
polymerized at a temperature below about 50° C., pref 10
erably 0° to» 30° C. Thereafter, the temperature is
Propylene was polymerized using the process of Ex
ample I except that the catalyst in Example II was
slowly raised at a rate not exceeding about 2° C. per
TiCl3-0.2AlCl3, in Example III was TiCl3-0.33AlCl3, and
minute to a ?nal temperature of between about 60 to 120°
in Example IV was TiCl2,8-0.24AlCl3. Also, toluene was
C., preferably 70 to 100° C. while continuing the pas
sage of alpha ole?n into the dispersion, and maintaining 15 used as the diluent in Example IV. The catalyst prepara
tion conditions, polymerization reaction conditions and
this temperature for from 1 to 10 hours, depending on the
the properties of the polypropylenes obtained are shown
rate of polymerization. A very slow rate of temperature
increase is not harmful but results in an unnecessary
in Table I.
the polymer from solution.
then increased at a rate of 2° C. per minute until the
temperature of about 99° C. was obtained. As can be
Examples V through VIII following illustrate the re
long induction period during which little or no polymeri
zation takes place. In general, therefore, a temperature 20 sults obtained when certain variations in the process are
adopted. The details therefore are given in Table I for
increase of from about 0.5 to 2° C. per minute is main
comparison purposes.
tained. During the above process the reaction mixture
is preferably stirred. When the desired degree of pol
ymerization has been obtained, a C1 to C8 alkanol such
Propylene was polymerized according to the process
as isopropyl alcohol or n-butyl alcohol, desirably in com 25
of Example II except that propylene was not introduced
bination with a chelating agent such as a 2,3- or 2,4
into the activated catalyst-xylene dispersion until the
diketone, e.g. acetyl acetone, is added to the reaction mix
dispersion was heated to 55° C. The temperature was
ture to dissolve and deactivate the catalyst and precipitate
After ?ltration, or other
physical removal of the polymer from solution, the poly
mer can be further washed with alcohol or an acid such
as hydrochloric acid, dried, compacted, and packaged.
seen from Table I, only 13 g. of polymer containing 8.3%
of waxy polymer was obtained. Additionally, only a low
catalyst ef?ciency was obtained due to severe catalyst
It is to be noted that the procedure given above is
critical with respect to the initial temperature at which
the alpha ole?n is added to the catalyst dispersion, and 35
the rate of temperature increase employed thereafter. If
Propylene was polymerized according to the process of
the alpha ole?n is added to the catalyst slurry at polymeri
Example II except that the triethyl aluminum activator
zation temperatures, very severe catalyst fouling occurs.
was not added to the propylene saturated TiCl3-0.2AlCl3
Likewise, if the rate of temperature increase is too rapid,
severe catalyst fouling also takes place. By catalyst foul 4 0 xylene slurry until the temperature was 74° C. Severe
catalyst fouling took place resulting in a yield ‘of solid
ing is meant the formation of a ?ocky or stringy catalyst
polymer of only 15 g. and a very low catalyst e?iciency.
which when used in the polymerization reaction results in
poor polymer yields and in the formation of polymers
Additionally, the polymer formed had a very low molecu
having poor physical properties.
The aromatic diluents useful in the present process are 4:5
lar weight.
aromatic hydrocarbon diluents such as benzene, toluene,
xylene and the like. Also, mixtures of these diluents can
Propylene was polymerized according to the process of
be used. However, xylene is superior to any of the other
Example 11 except that the temperature of the reaction
aromatic diluents in that higher rates of polymerization
mixture was raised at a rate of about 2.8° C. per minute.
are obtained therewith. Accordingly xylene is not equiva 50 This relatively rapid temperature increase resulted in cata
lent to other aromatic diluents although the use of other
lyst agglomeration and a decreased polymer yield.
aromatic diluents is within the broader scope of the in
vention. Aliphatic diluents cannot be used advantage
ously in the process since their use results in poorer pol
ymer yields and frequently also in agglomeration of the 55 ‘Propylene was polymerized according to the process of
Example 11 except that the activated catalyst was added
catalyst. and in severe polymer coating of the catalyst so
to ‘the propylene saturated xylene at 95° C. A very low
that very little catalyst activity is obtained thereby.
polymerization rate was obtained and accordingly the
The invention will be better understood by reference
experiment was terminated after 15 minutes. No polymer
to the following examples.
60 was recovered.
The following Examples IX through XI illustrate the
use of diluents other than xylene in the present process.
1.54 g. of a violet crystalline TiCl3 catalyst prepared
The catalyst preparation conditions, polymerization re
by the hydrogen reduction of TiCl4 at the surface of a
platinum ?lament at 700° C. was added to 100 ml. of
action conditions and the properties of the polypropylenes
xylene in a 2-liter stirred glass reaction ?ask. Then 2.24 65 obtained ‘are given in Table I.
g. Of'AlEtg was added and the resulting mixture stirred
for 30 minutes at 25° C. Thereafter, 400 ml. of xylene
was added to the mixture and gaseous propylene intro
Propylene was polymerized according to the process of
duced at a rate of about ‘1000 ml. per minute. The
Example I except that toluene-was used as the reaction
temperature was then increased at a rate of about 1° C. 70
diluent. The yield of polymer, the catalyst efficiency ob
per minute until a temperature of about 78° C. was
reached. The temperature was then maintained in the
tained and the tensile strength obtained, while all good,
were less than those of the process of Example I. How
ever, it can be seen that toluene is nevertheless operable
of. about 1000 ml. per minute. After the polymerization 75 as a diluent in the process, and accordingly this example
range of 78-80" C. for about 1.5 hours. During this
time, introduction of propylene was continued at the rate
illustrates the broader scope of the invention‘ which relates
to the use of aromatic diluents in general.
Propylene was polymerized according to the process
of Example I using a TiCl4~2AlEt3 catalyst mixture in
Propylene was polymerized according to the process of
xylene diluent. An extremely low yield of solid polymer
Example I except that in Example X n-heptane was used 5 and catalyst e?‘iciency as well as a relatively high percent
age yield of waxy polymer was obtained.
as a diluent and in Example X[ n-decane was used as a
diluent. In both of these examples the yield of solid
polymer, the catalyst e?iciency, and the tensile strength
Propylene was polymerized according to the process of
Example I except that a TiCl4-2AlEt3 catalyst mixture was
used in an n-decane diluent. Polypropylene having low
softening and melting point and a low tensile strength was
obtained as compared to the polypropylene of Example I.
Propylene was polymerized according tothe process
of Example I except that ‘a TiCl4-2AlEt3 catalyst mix
ture was used in an n-heptane diluent. Polypropylene
having a low molecular weight was obtained.
of the polymers obtained were all markedly less than in
Example I. Additionally, a higher percentage of waxy
polymer was obtained in both Examples X and XI.
The following Examples XII and XIV show that catalyst
systems made up of a reducible heavy transistion metal
compound and a reducing metal containing compound
cannot be used successfully in the present process either
in an aromatic or aliphatic diluent. The conditions of
preparation and polypropylene properties obtained are
given in Table I for comparison purposes.
Table I
Diluent __________________________________ __
Ex. I
Ex. 11
xylene _________ _-
xylene ___________ __
toluene __________ _-
Titanium ehloride—
Type _____ __
Weight, g_
1.81 ........... ._
Ex. V
TlCl2.s~0.24AlC13__ TlCl3-U.2A1C1a.
1 0
________ _.
g ______ __
Mixing Temp, ° C__
Time, Minutes___-
Catalyst Cone, g./l__
Al/Ti mole ratio;1 ____________________ .. 2
Reaction Conditions:
Vol 1
Starting Temp., ‘’ C ___________ ._
Polymerization Temp. Range, °
Polymerization time, hours ____ __
Catalyst Cone, g./1 __________ __
Max. absorption rate, ml./g./min_
Yield, g
Waxy péiiiéifb'e'rééiii?"
Catalyst e?‘iciency, gJg _____________ ._
Properties of Solid Polymer:
Molecular Wt. X 10-3 ________________ _.
Heptane insolubles, percent_.
Density, g./ml _________ __
Softening Point, ° C.
Melting Point, ° C
Tensile strength, p.s.1
Elongation, percent __________ _'_ ______ _.
Diluent ______________ __‘ __________________ __
Ex. VI
Ex. IX
Ex. X
xylene ___________ ..
xylene ........... __
xylene ___________ __
Titanium chloride-
Type ____________________________ __ T1Cl;.0.2A1C15._._ T1C13-0.2A1C13---. T1Cla-0.2AlCl3.- __
Weight, 2
1E g_
Mixing Temp., ° C
Time, Minutes__.__
_ 6O
Catalyst Conc., g./l
Reaction Conditions:
Al/Ti mole ratio 1
Vol., ___
Starting Temp, ° C
0.91 _____________ __
Polymerization Temp. Range, ° 0
._ 74
Polymerization time, hours ____ __
Catalyst Cone, g./1
Max. absorption rate, ml./g./min__ ___
Yield, g ______ __
Catalyst efficiency, g./g-_
Waxy polymer, percent.
Properties of Solid Polymer:
Molecular wt. X 10~3__
Heptane insolubles, percent-..
Softening Point, ° C
Density, g./ml
86.9-- .
_ __-__
___ ___
Melting Point, ° C__
Tensile strength, p.s.i__-_
Elongation, percent
1 Calculated on A1 in AlEl's only.
_ l
Table l —~Continued
Ex. XI
Dilnent ...................................... -.
n-deeane ........ __
xylene .......... ._
n-decane ________ __
Titanium chloride
8 _________________________________ __
Weight, g ____________________________ __
Mixing Temp, ° C
Time, Minutes _____ __
Catalyst 00110., g./l_
Al/Ti mole ratio 1 ___________ ..
Reaction 1Conditions:
Starting Temp., ° C
_______ n
Polymerization Temp. Range, ° C.-.
‘Polymerization time, hours. - ___
Catalyst Cone, g./l _________ __
Max. absorption rate, ml / [n1
Waxy polymer, percent
Catalyst e?iciency, g./g __________________ _.
Properties of Solid Polymer:
Molecular Wt. X 10-3 _____________________ __
113 ...... _
Heptane insolubles, percent
Density, g./n1l ______ __
Softening Point, °
Melting Point, ° C__
Tensile strength, p.s
Elongation, percent ______________________ __
l Calculated on Al in AlEta only.
It can be seen from Table I that the polymers of Ex 25 substantially atmospheric pressure, increasing said tem
perature at a rate not greater than 2° C. per minute until
amples I, II, III, IV and IX, the polymers of the inven
a polymerization temperature in the range of 60° to
tion, have very high tensile strengths. Additionally,
120° C. is ‘obtained while continuing the passage of said
they were found to be highly crystalline from X-ray dif
ole?n into said aromatic diluent, maintaining the poly
fraction studies. Also, the processes of these examples
show good yields and catalyst ef?ciencies and a relatively 30 merizat-ion temperature to polymerize propylene, and iso
lating said high crystallinity polymer therefrom.
low percentage of waxy polymer lay-product.
2. The process of claim 1 wherein the aromatic diluent
It is to be understood that the invention is not limited
is xylene.
to the speci?c examples which have been given by Way
References Cited in the tile of this patent
of illustration purposes only and that modi?cations herein
can be made without departing from the scope and spirit 35
of the invention.
Edwards et a1 __________ __ Feb. 18, 1958
What is claimed is:
Natta et al ____________ __ Apr. 14, 1959
1. The process for forming ‘a high crystallinity poly
Seelbach et al ___________ __ July 7, 1959
2,893,984. Kittleson
mer from propylene comprising the steps of passing said
_____________ __ Aug. 4, 1959
ole?n into an aromatic ‘hydrocarbon diluent containing 40 2,898,329
from 0.1 to‘ 0.5 wt. percent of a catalyst of ‘a cocrystallized
titanium trichloride-aluminum chloride activated with
from 0.1 to 5.0 mols of a trialkyl aluminum compound,
at a temperature in the range of 10 to 50° C., and at
Great Britain ___' ______ __ Dec. 11, 1957 _
Belgium ______________ __ Dec. 6, 1955
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