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Патент USA US3073821

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3,073,811
nP
United States Patent 0 1C6
Patented Jan. l5,_ 1963
2
l
However, even those supported catalyst systems have
rather limited activity and, moreover, favor the produc
tion of prevailingly or exclusively atactic polymers.
‘Surprisingly we have now found that catalysts contain
M973 Sill
PR?iIESS FOR PQLYMElé‘iZING ALPHA-QUEENS
AND CATALYST FOR USE THEREHN
Giulio Natta, l‘talo Pasquon, and Ettore Giachetti,
ing organo-metallic bonds, and consisting of the combi
Milan, Italy
No Drawing. Filed Apr. 14, 1951, Ser. No. 102,938
nationv of an alkyl compound of a metal of groups 11 or
Ill’v of' the periodic table (Mendeleetl) in which the alkyl
22 Claims. (Cl. Zed-$327)
radicals contain from 2 to 16 carbon atoms and prefer
ably triethylaluminum, a compound of a transition metal
for polymerizing alpha-ole?ns of the formula CH2=CHR, 10 of groups IV to VI of said table which is soluble in hy
drocarbon solvents and which when reacting with alkyl
where R is a hydrocarbon radical, to high molecular
compounds yields products soluble in hydrocarbon sol
weight, highly isotactic polymers, and to a new catalyst
vents, a crystalline, insoluble, low valency halide of a
for promoting the polymerization.
metal of groups IV to VI of said table, such as titanium,
It is known that when TiClr is reacted with an alumi
zirconium, vanadium and chromium, are more active as
num alkyl such as triethyl aluminum, at low temperature,
promoters of alpha-ole?n polymerization than any of
reduction of the TiCl, takes place, with formation of a
This invention relates to a new and improved process
the catalysts just described, and are highly stereospeci?c,
orienting the polymerization to the production of polym
erizates consisting prevailingly of isotactic macromole
cules. These new catalysts exhibit extraordinarily high
activity and, in general, remarkably increased stereo
mixture of diiierent compounds and complexes, and that
such mixture actively promotes the low~pressure polymer
ization of ethylene and diole?ns when the polymerization
is carried out in a hydrocarbon solvent in which the mix
ture is soluble.
speci?city, even when the amount of the soluble transi
tion metal compound used is small. The soluble corn<
pound may be used in an amount of 5% to 50%, pref
tion metals of groups IV to VI of the periodic table
(Mendeleeti) and alkyl compounds of metals of groups 25 erably 10%, by weight, based on the weight of the in
soluble crystalline transition metal halide such as tita~
1 to Ill of said table, promote the polymerization of pro
nium dichloride, titanium trichloride, or VCl3.
pylene and other alpha-ole?ns, in a hydrocarbon solvent
According to the present invention a molar ratio of
chemically inert to the catalyst, to a polymerizate com
the aluminum trialkyl to the insoluble compound in the
prising a mixture of head-to-tail high molecular weight
macromolecules having different steric structures. Some 30 range of 0.5 :1 to 10:1, preferably 1:1 to 4:1 may be used.
It is noteworthy that the activity of the present cata
of the macromolecules have a stereoregular structure
lysts is higher than the Natta et al. catalysts prepared
which Natta has identi?ed as the “isotactic” structure and
from insoluble, crystalline titanium halides in which the
others of the macromolecules have a random structure
titanium has a valency lower than the maximum valency
and are identi?ed by Natta as linear, regular head-to-tail
Natta et al. have disclosed their discovery that catalysts
prepared under given conditions from halides of transi
“atactic” macromolecules.
35
in general, catalysts of this type which are soluble in
the hydrocarbon solvent in which the polymerization is
carried out, and which are active promoters of ethylene
and diole?n polymerization, have only a scarce activity
in the polymerization of the alpha-ole?ns.
corresponding to its position in the periodic table, and
metal alkyls such as triethyl Muminum, which latter cata
lysts themselves exhibit good stereospeci?city and activ—
ity, as Natta et al. have shown.
As noted above, the soluble catalysts prepared from the
4.0 organometallic compounds of metals of groups 11 to Ill of
Natta et al. have also shown that, on the contrary,
the periodic table (Mendelee?) and soluble compounds
catalysts prepared from pure (violet) titanium trichloride
of transition metals of groups 1V to VI of said table only
and triethyl aluminum, and which are at least partially
insoluble in the polymerization solvent, are more active
exhibit any appreciable activity in the polymerization of
alpha-ole?ns when those catalysts are adsorbed on a
chain, and the hydrogen atoms bound to those carbon
The term “isotactic” de?nes the particular steric struc
ture in the macromolecules of the alpha-ole?n polymer
and’ is not synonymous with “crystalline,” since the iso
and insoluble transition metal halides are not only highly
active but exhibit, in spite of the increased activity there
of, an increased stereospeci?city which is different from
that of the former supported catalysts from soluble transi
tion metal compounds and results in the production of
tactic structure persists whether the polymer is in a crys
talline or non-crystalline state. Under appropriate con
of isotactic macromolecules.
in the polymerization of higher alpha-ole?ns and orient 45 highly adsorptive support like silica gel or alumina.
When used on the support, those catalysts orient the
the polymerization to the production of polymerizates
polymerization to the production of polymers having, pre
consisting prevailingly of macromolecules having substan
vailingly, the Natta atactic structure and which are non
tially the Natta “isotactic” structure, i.e., macromolecules
crystallizable under any conditions. It is particularly
comprising the structure characterized in that supposing
noteworthy and unexpected, therefore, that the present
the macromolecular main chain fully extended in a plane,
catalysts prepared from the alkyl metal compound, solu
the groups bound to the tertiary asymmetric carbon atoms
ble transition metal compound containing organic groups,
of adjacent monomeric units are on one side of the main
atoms are on the opposite side of the chain.
ditions, the isotactic macromolecules are crystalline and
isotactic polymers (i.e., polymers made up of isotactic
macromolecules) are highly crystalline polymers.
Natta et al. have disclosed, further, that soluble cata
lysts obtained by reacting certain compounds of transition
the crude polymerizates comprising the high proportion
This result can be explained by asuming that the
crystalline, insoluble transition metal halides, which have
per so no active centers for the‘ polymerization of alpha
ole?ns or have only a relatively limited number of them‘,
act as an ‘adsorptive support for the soluble complexes
metals containing organic groups, such as alkoxides, ace 65 resulting from the reaction of the metal alkyl and soluble
tylacetonates, etc. of the metals, with triethyl aluminum,
while promoting the polymerization of ethylene, do not
polymerize propylene in solution at practically acceptable
rates, but that those catalysts are somewhat more satis
transition metal compound. Such complexes which per
so are practically without catalytic action, become active
when they are chemically absorbed on the crystalline
halide surface, or at any rate increase the number of
factory promoters of propylene polymerization when they 70 active centers, or the activity of the centers already pres
are absorbed on a support having high absorptive charac
teristics, such as alumina, silica gel, etc.
eat on the surface of the titanium halide. Such stereo“
3
3,073,811
speci?city is not acquired by the soluble complexes when
allow of a regular di?usion of the monomer on the
catalyst surface, and if pure reactants are used.
they are adsorbed on an amorphous support, such as
silica gel or alumina. In the latter case, the polymeriza
tion of the alpha-ole?ns is oriented to the production of
EXAMPLE 1
atactic polymers.
We have further surprisingly found, that, not only
crystalline insoluble, low valency halides of titanium,
5
The catalyst is prepared by introducing the insoluble
crystalline titanium halide (TiClg), triethyl aluminum, the
soluble titanium compound (e.g. titanium isopropylate,
dichloro-dicyclopentadienyl-titanium, or titanium dichlo
vanadium and chromium can act as an adsorptive support
for the soluble complexes described, but that also solid
halides of transition metals of the VIII group of the 10 ro-diacetylacetonate) and 250 cc. of solvent (n-heptanc
periodic table, which are insoluble in hydrocarbon
or toluene) into a 500-cc. stainless steel oscillating auto
solvents and which have an analogous crystalline struc
clave under nitrogen. The autoclave is then evacuated
ture, although being per se, in the presence of metal _ and heated to the polymerization temperature. The gas
alkyls, inactive in the polymen'zation of the alpha-ole?ns,
eous monomer is introduced and the indicated partial
may be used as adsorptive supports for preparing the 15 pressure is then maintained constant.
present catalysts. An example of such crystalline halides
In order to determine the polymerization rate, the run
is cobaltous chloride.
is stopped only after the polymerization rate has reached
Polymerization of the alpha-ole?ns with the present >
a value which is practically constant with the time.
The crude polymerizates are extracted with hot ether
sure or at somewhat increased pressure, e.g., at pressures 20 to separate an amorphous, atactic fraction, then with hot
up to 10 atmospheres or higher, at a temperature of 10°
n-heptane to separate a partially crystalline, partially iso
C. to 100° C. and in a hydrocarbon solvent which may
tactic friction and leave a crystalline, isotactic residue.
be paraiiinic or aromatic.
The results of the run are shown in Table I and com
Titanium compounds which are soluble in the hydro
‘ pared with the results obtained using, with triethyl alu
carbons used as polymerization solvent and which may 25 minurn, only TiClz or only the soluble titanium com
catalysts is carried out under normal atmospheric pres
be used in preparing the present catalysts include titanium
pound. The values for the intrinsic viscosity given in
alkoxides and monohalogeno-alkoxides, halogen-acetyl
Table I were determined on the residue of the ether ex
traction.
acetonates of the type of titanium dichloro-acetyl
acetonate, acetyl acetonates such as titanium triacetyl
Table I also gives the results of polymerization runs
acetonate, acylhalogen compounds such as titanium 30 carried out with the use of triethyl aluminum and solid
chloride-acetates, alkoxy-acyl compounds such as alkoxy
acetates, and dicyclopentadienyls like dichlore-dicyclo
pentadienyl titanitun.
When the soluble transition metal compounds of the
types mentioned are reacted with a metal alkyl which is
titanium halide only, but in an amount corresponding to
about the sum of the weights of titanium halide and solu
ble titanium compound used in the other runs. The
activity of the present catalyst systems is even more clearly
apparent from a consideration of the results of the last
preferably an aluminum alkyl in which the alkyl radicals
mentioned runs.
contain from 2 to 16 carbon atoms, in the presence of a
EXAMPLE 2
crystalline insoluble transition metal halide such as tita
nium trichloride, titanium dichloride, vanadium tri
chloride, chromium trichoride and cobaltous chloride, the
activity of the resulting highly stereospeci?c catalysts is
The run was carried out as in Example 1, except that
40 titanium trichloride was used instead of titanium di
(after the ?rst moments of the reaction), practically con~
stant for many hours.
chloride. The results are shown in Table II, which shows
the same comparisons with runs performed under other
conditions as are given in Table 1.
The results we have obtained by polymerizing alpha
ole?n's with the aid of a catalyst prepared from soluble
titanium compounds in the presence of crystalline tita
nium tn'chloride or dichloride and triethyl aluminum are
EXAMPLE 3
A suspension of 0.20 g. crystalline TiCl3 in n~heptanc,
a solution of 0.1 cc. Ti(i-OC3H7)4 in n-heptane, and a
shown in Tables I and II, respectively.
solution of 1 cc. Al(C2H5)3 in n~heptane are introduced
From these tables, it is apparent that in some instances,
using only 10% by weight of the soluble titanium com 50 under vacuum into a 2,000-cc. stainless steel vertical auto
clave provided with a propeller stirrer and kept at 70°
pound (with respect to titanium chloride) the catalytic
C., n-heptane being then added up to 500 cc. Stirring
activity is increased up to 600% in relation to the activity
is initiated, and after ten minutes, gaseous propylene is
which is observed when the catalyst is prepared from a
introduced. The autoclave is kept under a pressure of 3
crystalline titanium halide and an alkyl aluminum com~
atm. during the entire reaction time. After 50 hours, the
pound, only. Moreover, both the crystallinity and the 55 reaction is stopped. 175 g. of polypropylene having the
molecular weight of the polymers obtained with the
following characteristics are obtained:
present catalyst system are always higher, or are always
at least equal to, the crystallinity and molecular weight
of the polymer obtained without the addition of soluble
transition metal complexes to the reacting system.
The following examples are given to illustrate the in~
vention, it being understood that these examples are not
intended as limiting. In these examples, the pressure was
Percent
Amorphous _________________________________ __ 16
Partially crystalline ___________________________ __ 5
Crystalline _________________________________ __ 79
A run carried out under the same conditions, but with
out the addition of the soluble alcoholate, gave an average
kept constant throughout the reaction period by feeding
production of 1.9 g./hour in the ?rst 45 hours, that is,
a production much lower than the average obtained in.
50 hours using the catalyst according to this invention.
the gaseous ole?n continuously into the reactor. In this
way, is was possible to follow the progress of the reaction
with time and to determine that the reaction rate, after
an initial state of a few tens of minutes during which it
changes with time, reaches standard values, expressed in 70
grams per hour of reacted monomer (i.e., of polymer
produced) as shown in Tables I and II. This activity
remains practically unchanged for many hours, if the free
volume of the reacting system and the amount of solvent
EXAMPLE 4
A suspension of 0.9 g. titanium trichloride in anhy—
drous n-heptane, a solution of 2 cc. aluminum diethyl
monochloride, and a solution of 0.2 g. titanium tetraiso
propylate in anhydrous n-heptane are introduced under
75 vacuum in a shaking, stainless steel autoclave of SOD-cc.
3,073,811
6
'5
TABLE III
capacity. Additional anhydrous n-heptane is introduced
Polymerization of butenegl with the aid of 1.5 g.
up to a total of 250 cc. The autoclave is brought to the
TiClg and 2 cc. Al(C2H5)3 in n-heptane at 15° C.
polymerization temperature (70° C.) and gaseous pro
and atmospheric pressure. Duration: 18 hours.
pylene is introduced up to a pressure of 1000 mm. mer
cury above atmospheric pressure, the pressure being kept 5
constant for the
entire duration of the~' run.
<
After
‘
Obtaine
hours, 15.5 g. of polymeuzate are obtained.
Run
(1
Percent soluble in—-
polybw Acetone
Operating under slrnilar conditions, but in the absence
tens, g_.
of
obtained.
titanium alcoholate, only 11.9 g. of polymerizate are 10
Ethyl
.
,_
after
11-Hep- extract
ether
ether Henna time
The intrinsic vrscosities ‘of the fractions of the polym-
1,_____
25.5
L8
163
23
erizates, which are insoluble in cold-n-heptane, are re-
2 _____ __
10.4
1
24.6
74.3
spectively
(in tetralin at 135° C.) 3.75
and 3.5, in both
@3563
V
[n]igrits.
us
[11 of
0t er
58.8’
0
L58
M
N.d.
3.24
~ 4‘ isopropylate
'7 ~
7 added.
10.4 a. titanium
TABLE I
Polymerization of Propylene to Isotactic Polymers With
Soluble Titanium Compounds, Crystalline Titanium
Dichloride and Triethyl Aluminum (Triethyl Alumi
num Used in Each Run: 2 cc.)
Crystalline
halide
(TiClz),
g.
____ __
Calls presTemp, sure mm.
° C.
Hg (abs.)1
Soluble titanium
compound, g.
‘Did-003131); 0.135..
1. 2
1. 2
Solvent,
250 cc.
Standard
absorption Reacrate, g.
tion
Cal-I6
time,
per
hour hours
_
Total
polymer
produced,
g.
Amorphous1
Partially
crystalline 1
.._-_..
Intrinsic vis
Highly
cosity of the
cryspartially cryst.
tallinc 1 eryst.
plus fraction,
highly
100 ce./g.
70
2,450
0
6
O
__._
__.__.
.._._._...__
70
70
2,450
2, 450
4. 9
7. 5
3
3
12.1
21.0
15. 6
15. 0
s
8
76. 4
77.0
3. 25
‘i. 25
13. 5
3. 26
1. s5
____________________ _-
70
2, 450
5. 4
3
15. 4
7.8
76. s
____
1. 2__
____________________
TlC12(C5H5)20.165___
70
1,4150
1,450
0
2. 7
63
0 95
3.
13. 0
7. 5
79. 5
3.40
1. 2
1.11
TiOl2(GsH5)z 0.165- .
____________________ ..
7o
70
1, 450
1, 450
13. 5
3. l
3
3
24.60
4.5
12. 5
13. 2
7. 4
7. 5
so. 1
9. 3
4.40
3. 38
____ __
TiClz(O5HrO2)20.3_.
70
1,450
0
6
_.__
_-_..__
_____-
____________
1. 2
"13101405117092 0.3. _
70
1, 450
8.2
3
0
24. 7
14. 0
3
7s
.......... -
1 Constant for the duration of the reaction.
TABLE II
Polymerization of Propylene to Isotactic Polymers With
Soluble Titanium Compounds, Crystalline Titanium
Triehloride and Triethyl Aluminum (Triethyl Alumi
num Used in Each Run: 2 cc.)
Grys
talline
AEquiSoluble ti-
CaHa
halide
tanium
(T1613),
compound
‘Did-003E041,
g
° 0.
g.
Intrinsic vis
librium Reaction
Temp, pressure,
mm. Hg
Total
Partially
Highly
Solvent,
absorp-
time,
polymer
Amor-
crystal<
crystal-
250 cc.
tron rate,
g- 01116
per
hour
hours
produced,
phous 1
line 1
line 1
(abs.)1
6
0
___ __
o, 09
7o
1, 450
n-Heptanc _ _.
__________ _-
70
1,450
_--.-do ..... _-
0. 79s
o. oo
70
1, 450
________
_____
0.36
70
450
0. 79s
__________ _-
0. 36
0.36
70
70
70
450
450
450
9. 7
9. 6
2
4
16. 5
34. o
4. 3
13. 4
11.1
10. 9
4. 4
3. 7
1. 15
1.15
__________ ..
__________ --
70
70
450
450
3- 6
3. 5
2
4
6. 3
13. 2
13. o
12. 6
6. 3
6. 2
a 2
14. 3
15.0
2
29. 9
13. 6
4. 5
__ _ _ __ _ _
_ _ _ _ _ __
(i
2. 5
0
2
1 Constant for the duration of the reaction.
plus highly
_ _ _ _ _ __
8. 4
15.1
0
part. cryst.
cryst.
100 fraction,
eoJg.
0. 79s
0. 79s
0. 798
0
g.
cosity of the
6.8
6.1
.
EXAMPLE 5
EXAMPLE 6
0.55 g. vanadium trichloride, 0.06 g. vanadium tri
1.5 g. titanium trichloride, 0.4 g. titanium tetraiso
propylate and 2 cc. triethyl aluminum are introduced in 60 acetyl acetonate and 0.6 cc. aluminum triethyl are intro
duced into a shaking stainless steel autoclave of 500 cc.
a shaking stainless steel autoclave of 500 cc. capacity
capacity in a nitrogen atmosphere.
under nitrogen.
Vanadium acetyl acetonate and aluminum triethyl are
The titanium alcohola to and the aluminum alkyl are
added in solution in anhydrous benzene, the solvent used
added in solution in anhydrous n-heptane, the total
amount of solvent being 100 cc. The autoclave is evac
amounting in total to 250 cc. The autoclave is‘ evac
uated and the temperature is adjusted to 15° C.; there-v
after gaseous l-butene is introduced up to atmospheric
pressure, which is kept constant for the duration of the
uated and brought to 70° C., which-temperature is kept
run.
H
,
7
_,constant for the duration of the run.
Gaseous propylene is then fed in up to a pressure‘ of
500 mm. of mercury above the normal pressure, which
After 18 hours, 25.5 g. polymerizate are obtained
which are extracted successively with the following hot
is kept constant for. the entire polymerization. After
21/2 hours, 11.5 g. of polymerizate are obtained and
extracted in succession with hot ether and hot n-heptane.
Table IV below gives the results obtained, in com
solvents: acetone, ethyl ether, hexane, and heptane.
In Table Ill below is shown the results obtained in
comparison with a run carried out without titanium
alcoholate.
75
parison with the run carried out under the same con
3,073,811
8
ditions but carried out in the absence of vanadium acetyl
acetonate.
‘70° C., and kept at this temperature. Propylene is then
'
,
added, up to a relative pressure of 1500 mm. (Hg) which
pressure is also kept constant during the run. The po
TABLE IV
Propylene polymerization with the aid of 0.25 g. TiCl3
lymerization is stopped after 31/2 hours.
A similar run is carried out, omitting the Ti triacetyl
and 0.6 cc. Al(C2H6)3 in benzene at 70° C. and
Propylene pressure (abs) 700 mm, Hg. Duration:
2% hours
Percent soluble in-
Run
Obtained
polymerizate, g.
1 1 _____ __
2 ______ __
11.5
9. 7
Ether
Residue
[1;] of resi
ni'tcr n-
duo after
heptane
4. 0
5. 5
Fractions obtained by extraction
of the crude W1‘ th boiling solvents
Intrinsic M
Polymerizate
g. obtained,
ether_ex_
n-Heptane extraction,
percent
19. 2
30.2
acetonate. The results obtained are as follows:
viscosity
traction
Ether, n-Hcptanc, Residue,
percent
76. 8
64. 0
With TlACs, 28.7 _______ _.
Without TiAc, 16.2 ____ __
3. 38
3. 20
3. 5G
3.21
7. 7
9. 2
percent
percent
G. 9
0. 9
85. 4
83. 0
Note.-'I‘iAc3——Titani1un triacetylacctonate.
EXAMPLE 10
0.61 g. of gamma TiCl3, 0.8 g. aluminum triethyl, 0.03
1 0.06 g. vanadium triacetyl acetonate added.
EXAMPLE 7
A suspension of 1.2 g. titanium dichloride in anhy
drous n-heptane, a solution of 0.15 g. chromium ace
tylacetonate and a solution of 2 cc. triethyl aluminum
in n-heptane, the total volume of solvent being 250 cc.
are introduced into a SOC-cc. shaking autoclave. The
temperature is brought to 70° C. and gaseous propylene
is added up to a pressure of 1450 mm. mercury. Poly
merization is carried out for 31/2 hours. At the end of
this time the reaction is stopped and 11.5 g. polypropyl
ene are obtained having the following characteristics:
g. titanium triacetylacetonate and 200 cc. toluene are in
troduced into the autoclave of Example 9. After heat
ing to 70° C., propylene is added up to a relative pressure
of 500 mm. (Hg). Temperature and pressure are kept
constant during the run which lasts 70 minutes.
A similar run is carried out, omitting the titanium tri
acetylacetonate. The results obtained are as follows:
Fractions obtained by extraction
Amorphous=13.5% (soluble in hot ethyl ether). The
Intrinsic oi the crude with boiling solvents
Polymeriznte obtained,
residue of the extraction with hot ethyl ether has an
g.
intrinsic viscosity of 3.9.
Operating in similar way, without the addition of
chromium acetylacetonate, only about 5 g. of crude po
viscosity
Ether, n-Hcptanc,
Residue,
percent
percent
percent
With TiAca, 18.5 ....... __
Without TiACs, 13.2 .... .-
lymerizate are obtained under the same conditions.
EXAMPLE 8
3. 7
3.4
10. 5
11.2
6. 2
8. 8
83.3
80.0
crystalline halide (cobaltous chloride or chromium tri
Similar results are obtained upon using as the soluble
transition metal component, the other soluble transition
chloride), triethylaluminum, the soluble titanium com
pound (titanium isopropylate) and 250 cc. n-heptane
into a SOO-cc. stainless steel shaking autoclave in nitrogen
acetylacetonates, acetylacetonates, chloroacetates, alkoxy
The catalyst is prepared introducing the insoluble
metal compounds of the present invention such as those
selected from the alkoxides, halogen alkoxides, halogen
atmosphere.
acetates and the chloro-dicyclopentadienyls of vanadium,
zirconium and chromium.
Results similar to those shown in the working examples
are also obtained when the corresponding alkyls of be
ryllium are utilized in place of the alkyls of aluminum.
In this case, polymerizates consisting essentially of iso
The autoclave is then evacuated and heated to the
polymerization temperature (70° C.) and gaseous
propylene up to an absolute pressure of 1450 mm. mer
cury which is then kept constant.
After 18 hours, the polymerization is stopped and
the reaction product is extracted and puri?ed as usual.
The puri?ed polymerizate is then extracted in suc
tactic macromolecules are obtained.
The present catalysts are effective promoters of the
polymerization of the alpha-ole?ns CH2==CHR in which
cession in boiling ether and n-heptane.
R is a hydrocarbon radical containing from 1 to 16 car
bon atoms.
In Table V results of polymerization runs carried out
using cobaltous or chromium chlorides supports are
The stability of these new catalysts, which is manifested
in the continued, constant activity of the catalysts over
given.
TABLE V
Polymerization of propylene with catalysts from tita
nium isopropylate, dicobaltous chloride or chromium
trichloride and triethyl aluminum
Extraction
Run
Crystalline
Ti(i-OC3H7)4,
Al(C2H5)a,
Dura-
chloride, g.
g.
cm.3
tion,
hours
2
2
18
18
2
18
2
18
2
1S
Total
polymer, Soluble Soluble
g.
in other, in n>nep- Residue,
percent
tune,
percent
percent
46 8
42 3
_
12. 6
19
‘l0. 6
38. 7
-_-.
2
N.
-
N .d
______________________________________ __
EXAMPLE 9
039g. of alpha~TiCl3, 1.16 g. aluminum triethyl, 0.039
'g. titanium triacetyl acetonate and 200 cc. toluene are ,
,many hours after the ?rst moments of the reaction, is in
‘marked contrast to the progressive loss of activity gen
erally observed with catalysts prepared from heavy metal
introduced into a 500-cc. autoclave which is heated to 75 compounds
and metal alkyls.
3,073,811
Some changes and variations may be made in details in
practicing the invention, without departing from the spirit
thereof, and we intend to include in the scope of the ap
pended claims all such modi?cations as may be apparent
to those skilled in the art.
The present application is a continuation-in-part of
application Serial No. 716,527, ?led February 21, 1958.
Having thus described the present invention, what it is
10
7. A process according to claim 1, wherein the catalyst
consists of a hydrocarbon soluble halo-acyl compound
of (1), a metal alkyl compound of (2) and a solid crystal
line low valency halide of (3).
8. A process according to’ laim 1, wherein the catalyst
consists of a hydrocarbon soluble alkoxy-acyl compound
of (l), a metal alkyl compound of (2) and a solid crystal
line low valency ‘halide of (3).
9‘. A process according to r laim 1, wherein the catalyst
desired to secure and claim by Letters Patent is:
consists of a dicyclopentadienyl of (l), a metal alkyl com
10 pound of (2) and a solid crystalline ‘low valency halide
What is claimed is:
l. A process for polymerizing .alpha-ole?ns of the
of (3).
formula CH2=CHR wherein R is a hydrocarbon radical,
10. A process according to claim 1, wherein the cata
to high molecular weight linear polymers, which process
lyst consists of a titanium compound of (1), a metal alkyl
comprises polymerizing the monomer in a hydrocarbon
compound in which the alkyls contain from 2 to 16 carbon
solvent and in contact with a catalyst containing organo
atoms and selected from the group‘ consisting of aluminum
metallic bonds and consisting of the combination of
and beryllium alkyl compounds, and a solid crystalline
(1) a transition metal compound soluble in the hy
low valency halide of (3).
drocarbon solvent and selected from the group con
11. A process according to claim 1, wherein the cata
sisting of alkoxides, monohalo-alkoxides, halo-ace
lyst consists of a vanadium compound of (1), a metal
tylacetonates, acetylacetonates, halo-acyl compounds,
alkyl compound in which the alkyls contain from 2 to 16
allooXy-acyl compounds and dicyclopentadienyls of
carbon atoms and selected from the group consisting of
titanium, vanadium, zirconium and chromium,
aluminum and beryllium alkyl compounds and a solid,
(2) an alkyl compound of a metal of groups 11 and
crystalline low valency halide of (3).
HI of the Mendeleeff periodic table in which the
12. A process according to claim 1, wherein the cata
25
alkyl groups contain from 2 to 16 carbon atoms,
lyst consists of a chromium compound of (1), a metal
said transition metal compound of (1) being further
alkyl compound in which the alkyls contain from 2 to 16
characterized in that by reaction with the said metal
carbon atoms and selected from the group consisting of
alkyl compound of (2), it yields products soluble in
the hydrocarbon solvent, and (3) a solid, crystalline
low valency halide selected from the group consist
ing of halides of titanium, zirconium, vanadium,
chromium and cobalt in which halide the metal has
aluminum and beryllium alkyl compounds and a solid,
crystal-line low valency halide of (3).
13. A process according to claim 1, wherein the cata
lyst consists of a titanium compound of (1), triethyl alumi
num and solid, crystalline titanium dichloride.
14. A process according to claim 1, wherein the cata
‘lyst consists of a titanium compound of (1), triethyl alumi
metal alkyl compound of (2), it yields products 35 num and solid, crystalline titanium trichloride.
15. A process according to claim 1, wherein the cata
which are at least partially insoluble in the hydro-'
lyst consists of a titanium compound of (1), diethyl alumi
carbon solvent.
2. A process according to claim 1, characterized in
num =monochloride and solid, crystalline titanium di
that the catalyst contains from 5% to 50% by weight of
chloride.
16. A process according to claim 1, wherein the cata
the hydrocarbon soluble transition metal compound, based 40
lyst consists of a titanium compound of (1), diethyl alumi
on the weight of the crystalline low valency metal halide,
num monochloride and solid, crystalline titanium tri
the molar ratio of the metal alkyl compound to the crys
talline low valency halide is from 0.521 to 10:1, and the
chloride.
17. A process according to claim 1, wherein the cata
polymerization of the monomer in contact with the cat
45
lyst consists of a vanadium compound of (1), triethyl
alyst is carried out at a tempearture of about 10° C. to
a valence not higher than 3, said halide being fur
ther characterized in that when mixed with the said
about 100° C. and under a pressure of from normal at
aluminum and solid, crystalline vanadium trichloride.
18. A process according to claim 1, wherein the catalyst
mospheric pressure to 10 atmospheres pressure.
consists of a chromium compound of (1), triethyl alumi
3. A process according to claim 1, wherein the catalyst
num and a solid, crystalline titanium chloride.
consists of a hydrocarbon soluble alkoxide of (1), a metal
19. A process according to claim 1, wherein the cata
alkyl compound of (2) and a solid, crystalline low valency 50
lyst
consists of a titanium compound of (1), triethyl alumi
halide of (3).
4. A process according to claim 1, wherein the catalyst
num and solid, crystalline cobaltous chloride.
20. A process according to claim 1, wherein the cata
consists of a hydrocarbon soluble mono-halo-alkoxide of
lyst consists of titanium dihalo-dicyclopentadienyl, an
(1) a metal alkyl compound of (2) and a solid crystalline
aluminum alkyl and solid, crystalline titanium trichloride.
low valency halide of (3).
21. A process according to claim 1, wherein the cata
5. A process according to claim 1, wherein the catalyst
lyst consists of titanium triacetylacetonate, an aluminum
consists of a hydrocarbon soluble halo-acetylacetonate of
alkyl and solid, crystalline titanium trichloride.
(1), a metal alkyl compound of (2) and a solid crystalline
22. A process according to claim 1, wherein the cata
low valency halide of (3).
60
lyst consists of titanium tetraisopropylate, an aluminum
6. A process according to claim 1, wherein the catalyst
alkyl and solid, crystalline titanium trichloride.
consists of a hydrocarbon soluble acetylacetonate of (1), a
metal alkyl compound of (2) and a solid crystalline low
No references cited.
valency halide of (3).
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No, 3,073,811
January 15, 1963
Giulio Natta et a1°
It is hereby certified that error appears in the above numbered pat
ent requiring correction and that the said Letters Patent should read as
corrected below.
In the grant, lines 1 and 2, for "Giulio Natta, ltalo
Pasquon, and Ettore Giachetti, of Milan, Italy," read
—— Giulio Natta, Italo Pasquon, and Ettore Giachetti, of
Milan, Italy, assignors to Montecatini Societa Generals per
l‘lndustria Mineraria e Chimica, of Milan, Italy, ——>; line 11,
for "Giulio Natta, Italo Pasquon, and Ettore Giachetti,
their heirs" read —— Montec'atini Societa Generale per
l’Industria Mineraria e Chimica, its successors —-,; in the
heading to the printed specification, lines 4 and 5, for
"Giulio Natta, Italo Pas-quon, and Ettore Giachetti, Milan,
Italy" read —— Giulio Natta, Italo Pasquon, and Ettore
Giachetti, Milan, Italy, assignors to Montecatini Societa
Generale per I'Industria Mineraria e Chimica, Milan, Italy ——,
Signed and sealed this 20,th day of August 1963,
(SEAL)
Attest:
ERNEST W. SWIDER
DAVID L. LADD
.Atttestinigr Officer
Commissioner of Patents
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