Note: Descriptions are shown in the official language in which they were submitted.
12~91~2
CATALYST PREPARED FROM ORGANOMAGNESIUM COMPOUND,
ORGANIC HYDROXYL-GONTAINING COMPOUND, REDUCING HALIDE
SOURCE AND A TRANSITION METAL-O~GANOZINC COMPLEX
This invention relates to a new catalyst
composition useful for polymerization of one or more
~=olefins and to a polymerization process employing
such a catalyst composition.
It is well known that olefins such as ethylene,
propylene, and l-butene in the presence of metallic
catalysts, particularly the reaction products of organo-
metallic compounds and transition metal compounds, can
be polymerized to form substantially linear polymers of
relatively high molecular weight. Typically such
polymerizations are carried out at relatively low
temperatures and pressures.
Among the methods for producing such linear
olefin polymers are those described in U.S. Patents
3,113,115 and 3,257,332 using a catalyst obtained by
admixing a compound of a transition metal of Groups 4b,
5b, 6b and 8 of Mendeleev's Periodic Table of Elements
with an organometallic compound. Generally the halides,
oxyhalides and alkoxides or esters of titanium, vanadium
and zirconium are the most widely used transition metal
- 30,178A-F -1-
4;~
~2~31~:2
compounds. Common examples of the organometallic
compounds include the hydrides, alkyls and haloalkyls
of aluminum, alkylaluminum halides, Grignard reagents,
alkali metal aluminum hydrides, alkali metal boro-
hydrides, alkali metal hydrides and alkaline earthmetal hydrides.
Usually, the polymerization is carried out in
a reaction medium comprising an inert organic liquid,
e.g., an aliphatic hydrocarbon. One or more olefins
may be contacted with the catalyst in the reaction
medium in any suitable manner. A molecular weight
regulator, such as hydrogen, is often added. Such
polymerization processes are either carried out at
slurry polymerization temperatures where the polymer is
l not dissolved in the hydrocarbon reaction medium or at
solution polymerization temperatures where the temperature
is high enough to solubilize the polymer in the reaction
medium. Following polymerization, it is common to
remove catalyst residues from the polymer by treating
the polymer with alcohol or other deactivating agent.
Gessell, U.S. Patents 4,244,838, ~,246,383
and 4,387,200, disclose catalysts prepared by employing
an organic hydroxyl-containing material. However, such
catalysts must be separated from the liquid portion and
washed. It would be desirable to employ a catalyst
which does not require the recovery of the solid reaction
product and the attendant washing steps.
The present invention provides a catalyst for
polymerizing ~=olefins which is sufficiently efficient
that removal from the polymer is not required. Also
preparation does not require recovery and washing of
the solid reaction product nor is heating required.
30,178A-F -2-
ZAP
The present invention is directed to the
catalytic product resulting from admixing in an inert
hydrocarbon diluent and in an atmosphere which excludes
moisture and oxygen
(A) at least one hydrocarbon soluble organo-
magnesium material;
(B) at least one organic alcoholic hydroxyl
containing material;
(C) at least one reducing halide source; and
(D) the reaction product or complex formed by
mixing at a temperature and for a time suffi-
cient to provide a color change
(1) at least one transition metal (Tm)
compound having at least one hydrocar-
byloxy attached to said transition metal
and
(2) at least one organozinc compound; and
wherein
(a) the components are added in the
order (A), (B), (C) and (D) or (A),
(By, (D) and (C); and
(b) the components are employed in
quantities which provide the following
atomic ratios:
Mg:Tm of 0.1:1 to 100:1, preferably
1:1 to 40:1 and most preferably
5:1 to 20:1;
Zn:Tm of 0.05:1 to 10:1, preferably
- 0.1:1 to 5:1 and most preferably
0.2:1 Jo 2:1
Cl:Mg of 2:1 to 20:1, preferably
3:1 to 15:1 and most preferably
4:1 to 10:1; and
30,178A-F -3-
l2a.~
the OH:total number of hydrocarbyl
groups attached to a metal
atom in component (A) is 0.5:1
to 1.5:1 and preferably 0.8:1
to 1.2:1~
A further aspect of the invention is a process
for polymerizing ~=olefins or mixtures thereof which
comprises conducting the polymerization in the presence
of the aforementioned catalysts.
Organomagnesium materials suitably employed
in the present invention include those of the formula
R2Mg xMeR'x, wherein each R is independently a hydrocarbyl
group and each I' is independently a hydrogen, hydrocarbyl
or hydrocarbyloxy group, Me is Al, Zn or B, x has a
value from O to 10 and x' has a value equal to the
valence of Me.
The term hydrocarbyl refers to a monovalent
hydrocarbon group such as alkyl, cycloalkyl, aryl,
aralkyl, alkenyl and similar hydrocarbon groups having
from 1 to 20 carbon atoms with alkyl having from l to
10 carbon atoms being preferred. The term hydrocarbyloxy
refers to monovalent oxyhydrocarbon group such as
alkoxy, cycloalkoxy, aryloxy, aralkoxy, alkenoxy and
similar oxyhydrocarbon groups having from 1 to 20
carbon atoms with alkoxy groups having from to 10
carbon atoms being the preferred hydrocarbyloxy groups.
The quantity of MeR'x, , i.e. the value of x,
is preferably the minimum amount sufficient to render
the magnesium compound soluble in the inert solvent or
diluent which is usually a hydrocarbon or mixture of
30,178A-F -4-
lZ2
hydrocarbons The value of x therefore is from zero to
10, usually 0.2 to 2.
Particularly suitable organomagnesium compounds
include, for example, di-(n~butyl) magnesium, n-butyl-
-sec-butyl magnesium, diisopropyl magnesium, di-n~hexyl
magnesium, isopropyl-n-butyl magnesium, ethyl-n-hexyl
magnesium, ethyl-n-butyl magnesium, di-(n-octyl) magnesium,
butyl octyl magnesium and such complexes as di-n-butyl
magnesium-1/3 aluminum triethyl, di-(n-butyl) magnesium-1/6
aluminum triethyl, dibutylmagnesium 1/2 triisobutylaluminum,
butylethylmagnesium-1/2 triisobutylaluminum, butylethyl-
magnesium-l/4 triisobutylaluminum, di-n-hexylmagnesium--
1/2 triisobutylaluminum, and mixtures thereof.
Suitable alcoholic hydroxyl-containing organic
compounds include, for example, alcohols, glycols,
polyoxyalkylene glycols, and mixtures thereof.
Particularly suitable are compounds of the formulas
.
~nOH and Z~tO-R'~ O-R")
wherein each R is a hydrocarbyl group having from 1 to
20, preferably from 1 to 10, carbon atoms; each R' is
independently a divalent hydrocarbyl group having from
1 to 20, preferably from 1 to 10, carbon atoms; each R"
is independently hydrogen or a hydrocarbyl group having
from 1 to 20, preferably from 1 Jo 10, carbon atoms, at
least one of which is hydrogen; Z is a multivalent
o-rganic group containing from 2 to 20 carbon atoms;
n has a value from zero to 10; and n' has a value of
from 2 to 10.
^ 30,178A-F -5-
9~Z~
Typical organic hydroxyl-containing compounds
include alcohols such as methyl alcohol, ethyl alcohol,
n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, octyl alcohol,
octadecyl alcohol, glycols, 1,2-butylene glycol,
1,3-propylene glycol, 1,4-butanediol, 1,6-hexane diol,
other hydroxyl containing compounds such as glycerine,
trimethylol propane, hexanetriol, phenol, 2,6-di-tert-
-butyl-4-methylphenol, and mixtures thereof. Also
suitable are the adducts of ethylene oxide, 1,2 propylene
oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene
oxide or mixtures of such oxides with the previously
mentioned or other hydroxyl-containing compounds such
as pentaerythritol, sucrose, or sorbitol, as well as
alkyl and aryl capped hydroxyl-containing compounds
having at least 1 hydroxyl group per molecule.
Suitable reducing halide sources include
those of the formulas
Al~R3)3 mXm and B(R )3-mXm
including mixtures thereof wherein each R3 is indepen-
dently hydrogen or a hydrocarbyl group as hereinbefore
defined, X is a halogen, and m has a value from 1 to 2.
Particularly suitable reducing halides include,
ethylaluminum dichloride, diethylaluminum chloride,
25. e~hylaluminum sesquichloride, ethylboron dichloride,
diethylboron chloride, and mixtures thereof.
Suitable zinc compounds which can be advan-
tageously employed are those of the formulae R2Zn or
RZnX wherein each R is independently a hydrocarbyl
30,178A-F -6-
lZ~9~Z2
group having from 1 to 20, preferably from 1 to 10,
carbon atoms and X is a halogen, preferably chlorine or
bromine. Particularly suitable zinc compounds include
diethyl zinc, diphenyl zinc, ethyl zinc chloride, and
mixtures thereof.
Suitable transition metal compounds which can
be employed include those of the formulae Tm(OR'')nXz n
or Tm(OR")2O, wherein Tm is a transition metal in its
highest stable valence state selected from Groups IV-B,
V-B and VI-B of the Periodic Table of the Elements;
each R" is a hydrocarbyl group having from 1 to 2Q,
preferably from 1 to about 10, carbon atoms; X is a
halogen, preferably chlorine or bromine; z has a value
corresponding to the valence of the transition metal,
Tm; n has a value of from one to the valence state of
the transition metal, Tm.
Particularly suitable transition metal compounds
include tetraethoxytitanium, tetraisopropoxytitanium,
tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetra-
-(2-ethylhexoxy~titanium, tetraphenoxytitanium, tetra-
butoxyzirconium, tri-n-butoxy vanadium oxide, tri-
-isopropoxy vanadium oxide, zirconium tetra-n-propoxide,
zirconium tetraisopropoxide, and mixtures thereof.
When preparing the catalysts, it is particularly
advantageous to employ the organozinc-transition metal
complex in a pre-mixed form most advantageously formed
by the addition of one compound to the other in a
hydrocarbon solvent. Typical commercially available
organozinc compounds are dissolved in hydrocarbon
solvent. The concentration of the components and
temperature of mixing determine the time necessary for
30,178A-F -7-
}912~
a distinct color change. The color change varies
depending on the particular components employed.
Suitable organic inert diluents in which the
catalyst can be prepared and in which the ~=olefin
polymerization can be conducted include liquefied
ethane, propane, isobutane, n-butane, isopentane,
n-pentane, n-hexane, the various isomeric hexanes, iso-
octane, paraffinic mixtures of alkanes having from 8 to
12 carbon atoms, cyclohexane, methylcyclopentane,
dimethylcyclohexane, dodecane, eicosane, industrial
solvents composed of saturated or aromatic hydrocarbons
such as kerosene, naphthas, etc., especially when freed
of any olefin compounds and other impurities, and
especially those having boiling points in the range
from -50 to 200C. Also included as suitable inert
diluents are benzene, toluene, ethylbenzene, cumene,
and decalin.
uitable cocatalysts or activators with which
the catalysts of the present invention can be employed
in the polymerization of ~=olefins include aluminum,
boron, zinc or magnesium compounds of the formulas
Al(R )3_aX a B(R3)3_aX'a , MgR32 MgR3X', ZnR32 or
mixtures thereof wherein R3 is as previously defined;
X' is a halogen, preferably chlorine or bromine; and a
has a value of from zero to 2, preferably zero to 1 and
most preferably zero. Particularly suitable cocatalysts
or activators include diethylaluminum chloride, ethyl-
aluminum dichloride, diethylaluminum bromide, triethyl-
aluminum, triisobutylaluminum, tri-n-octylaluminum,
diethylzinc, dibutylmagnesium, butylethylmagnesium,
butylmagnesium chloride, diisobutylaluminum hydride,
isoprenylaluminum, triethylboron, trimethylaluminum,
and mixtures thereof.
30,178A-F -8-
~2~ 2
The cocatalysts or ac-tivators are employed in
quantities such that the atomic ratio of the Al, B, Mg,
Zn or mixtures thereof to TM is from 0.1:1 to 1000:1,
preferably from 5:1 to 500:1 and most preferably from
10:1 to 200:1.
The catalyst and cocatalyst or activator may
be added separately to the polymerization reactor or
they may be mixed together prior to addition to the
polymerization reactor.
Olefins which are suitably homopolymerized or
copolymerized in the practice of this invention are
generally any one or more of the aliphatic ~=olefins
such as, ethylene, propylene, butene-l, pentene-l,
3-methylbutene-1, 4-methylpentene-1, hexene-l, octene-l,
dodecene-l, octadecene-1, and 1,7-octadiene. It is
understood that ~=olefins may be copolymerized with one
or more other ~=olefins and/or with small amounts i.e.,
up to about 25 weight percent based on the polymer, of
other polymerizable ethylenically unsaturated monomers
such as styrene, ~=methylstyrene and similar ethylenically
unsaturated monomers which do not destroy conventional
Ziegler catalysts. Most benefits are realized in the
polymerization of ali.phatic ~=monoolefins, particularly
ethylene and mixtures of ethylene and up to 50 weight
percent, especially from 0.1 to 40 weight percent of
propylene, butene-l, hexene-l, octene-l, 4-methylpentene-1,
1,7-octadiene or similar ~=olefin or ~=diolefin based
on total monomer.
In practice, polymerization is effected by
adding a catalytic amount of the catalyst composition
30,178A-F -9-
--10
l~,t91.Z2
to a polymerization zone containing ~=olefin monomer,
or vice versa. The polymerization zone is maintained
at temperatures in the range from about 0 to 300C,
preferably at slurry polymerization temperatures from
about 0 to 95C, more preferably from 50 to 90C, for
a residence time of about 15 minutes to 24 hours, preferably
from 30 minutes to 8 hours. It is generally desirable
to carry out the polymerization in the absence of
moisture and oxygen.
A catalytic amount of the catalytic reaction
product is generally within the range from 0.0001 to
0.1 milligram-atoms transition metal per liter of
diluent. It is understood, however, that the most
advantageous catalyst concentration will depend upon
polymerization conditions such as temperature, pressure,
diluent and presence of catalyst poisons and that the
foregoing range is given to obtain maximum catalyst
yields. Generally in the polymerization process, a
carrier which may be an inert organic diluent or excess
monomer is employed. To realize the full benefit of
the high efficiency catalyst care must be taken to
avoid oversaturation of the diluent with polymer. For
best results, that the amount of polymer in the carrier
should not exceed about 50 weight percent based on the
total weight of the reaction mixture.
The polymerization pressures preferably
employed are relatively low, e.g., from 170 to 3550 kPa
(10 to 500 psig). However, polymerization within the
scope of the present invention can occur at pressures
from atmospheric up to the capabilities of the
polymerization equipment. During polymerization it is
desirable to agitate the polymerization recipe to
30,178A-F -10-
~z~ z
- obtain better temperature control and to maintain
uniform polymerization mixtures throughout the
polymerization zone.
Hydrogen is often employed to control the
molecular weight of the resultant polymer. For the
purpose of this invention, it is beneficial to employ
hydrogen in concentrations ranging from 0 to 80 volume
percent in the gas or liquid phase in the polymerization
vessel with the larger amounts of hydrogen producing
generally lower molecular weight polymers. Hydrogen
can be added with a monomer stream to the polymerization
vessel or separately before, during or after addition
of the monomer but during or before the addition of the
catalyst. Using the general method described, the
polymerization reactor may be operated liquid full or
with a gas phase and at solution or slurry polymerization
conditions.
The monomer or mixture of monomers is contacted
with the catalytic reaction product in any conventional
manner, preferably by bringing the catalyst composition
and monomer together with intimate agitation provided
by suitable stirring or other means. Agitation can be
continued during polymerization. In the case of more
rapid reactions with more active catalysts, means can
be provided for refluxing monomer and solvent, if any
of the latter is present and thus remove the heat of
reaction. In any event, adequate means should be
provided for dissipating the e~othermic heat of
polymerization, e.g., by cooling reactor walls, etc.
If desired, the monomer can be brought in the vapor
phase into contact with the catalytic reaction product,
in the presence or absence of liquid material. The
30,178A-F -11-
-12-
~2~9122
polymerization can be effected in a batch manner, or in
a continuous manner, such as, for example, by passing
the reaction mixture through an elongated reaction tube
which is contacted externally with suitable cooling
medium to maintain the desired reaction temperature, or
by passing the reaction mixture through an equilibrium
overflow reactor or a series of the same.
The polymer is readily recovered from the
polymerization mixture by driving off unreacted monomer
and solvent if any is employed. No further removal of
impurities is required. Thus, a significant advantage
of the present invention is the elimination of the
catalyst residue removal steps. In some instances,
however, it may be desirable to add a small amount of a
catalyst deactivating reagent. The resultant polymer
is found to contain insignificant amounts of catalyst
residue.
The following examples are given to illustrate
the invention, and should not be construed as limiting
its scope. All parts and percentages are by weight
unless otherwise indicated.
In the following examples, the melt index
value I2 was determined by ASTM D 1238 condition E.
The apparent bulk density was determined as an unsettled
bulk density according to the procedure of ASTM 1895
employing a paint volumeter from the Sargent-Welch
Scientific Company (catalog no. S 64985) as the cylinder
instead of the one specified by the ASTM procedure.
30,178A-F -12-
-13-
~Z~9~Z
GENERAL PROCEDURE
In each of the following examples, unless
otherwise stated, the catalyst components were blended
while in a gloved box filled with dry oxygen-free
nitrogen.
In the examples, the dibutylmagnesium was a
commercial material obtained as a solution in a heptane-
hexane mixture from the Lithium Corporation of America,
and the butylethylmagnesium was a commercial material
obtained as a heptane solution from Texas Alkyls, Inc.
All ratios are molar ratios unless otherwise indicated.
The 1.53 molar ethylaluminum dichloride, 0.616 molar
triisobutylaluminum and 0.921 molar triethylaluminum
were obtained as solutions in hexane from Ethyl
15 Corporation or Texas Alkyls, Inc.
.,
EXAMPLE 1
A. Catalyst Preparation
To a stirred 500 ml container were added
sequentially 32. 5 ml of 0.769 molar dibutylmagnesium
20 (25.0 mmoles), 20.3 ml of 0.616 molar triisobutylaluminum
(ATB) (12.5 mmoles), and 7.0 ml of neat n-propyl alcohol
(93.1 mmoles). The alcohol was added at a rate so as
to maintain temperature at about 40-50C. A clear
colorless solution resulted. The solution was cooled
25 to 18C and then 34.0 ml of 1.53 molar ethylaluminum
dichloride (EADC) (52.0 mmoles) were added dropwise so
as to maintain temperature at about 18-20C, resulting
in a white slurry. This was followed by the dropwise
addition at 20C of a pre-mixed solution containing 2.3
30 ml of 1.08 molar diethylzinc (DEZ) (2.48 mmoles) and
1.5 ml of tetraisopropoxytitanium (4.98 mmoles). The
DEZ:titanium mixture was pre-mixed one hour ~3600 s)
prior to use. The addition of the DEZ:titanium pre-mix
30,178A-F -13-
-14-
lZ~
resulted in a catalyst slurry which was tan-gold in
color. The atomic ratios of Mg:Ti, Cl:Mg, and Zn:Ti
were 5:1, 4.2:1, and 0.5:1, respectively. The molar
ratio of alcohol to alkyl groups attached to magnesium
and aluminum was 1.06:1.
B. Polymerization of Ethylene
To a stirred 1.0 liter reactor containing 600
ml of dry, oxygen free hexane were added (under nitrogen
purge) 2.4 ml of 0.921 M triethylaluminum (ATE) (2.210
mmoles) and an aliquot of catalyst, prepared in A
above, containing 0.0112 mmoles titanium. The ratio of
cocatalyst Al:Ti was 197:1. The reactor was sealed and
the nitrogen removed. The reactor contents were adjusted
to 85C and hydrogen added such that the total pressure
of the reactor was 70 psig (482.6 kPa).
Then ethylene was added to the reactor and
was used to maintain the reactor at 170 psig (1172.1
kPa) total pressure for 2 hours (7200 s). The reactor
was cooled, the seal broken, and the contents removed.
The contents were filtered and dried in a vacuum oven
at 60C. The polyethylene obtained weighed 244 grams,
had a bulk density of 20.2 lb/ft3 (0.324 g/cc), and a
melt index, I2, of 3.6. The catalyst efficiency was
454,000 g PE/g Ti.
C. Polymerization of Ethylene
A polymerization of ethylene was made according
to the procedure of 1-B, except that triisobutylaluminum
(ATB) was substituted for triethylaluminum (ATE) as
cocatalyst. 2.4 ml of 0.616 M ATB ~1.478 mmoles) and an
aliquot of catalyst 1-A containing 0.0144 mmoles titanium
were used. The cocatalyst Al:Ti ratio was 103:1. The
30,178A-F -14-
-15-
12~C~l~Z
dried polyethylene weighed 154 g, had a melt index of
0.9, and a bulk density of 19.1 lb/ft3 ~0.306 g/cc).
Catalyst efficiency was 223,000 g PE/g Ti.
EXAMPLE 2
A. Catalyst Preparation
To 39.2 ml (25.0 mmoles) of 0.637 M of butyl-
ethylmagnesium in heptane were added sequentially 20.3
ml (12.5 mmoles) of 0.616 M triisobutylaluminum in
hexane, and 6.5 ml (87.5 mmoles) of n-propyl alcohol.
The temperature of alcohol addition was about 40C.
The resultant clear, colorless solution was cooled to
20C, and then 32.7 ml (50 mmoles) of 1.53 M ethylaluminum
dichloride in hexane were added dropwise so as to
maintain temperature at 25C. A white solid formed
after the addition of ethylaluminum dichloride. Then 5
ml of a pre-mixed 0.5 M hexane solution of diethylzinc
and tetraisopropyltitanate, containing 2.5 mmoles of
tetraisopropoxytitanium and 2.5 mmoles of diethyl~inc,
were added dropwise. The solids color changed to tan,
and a small exotherm to 27C was noted. The final
atomic ratios in the catalyst were Cl:Mg=4:1~ Mg:Ti=10:1,
Zn:Ti=1:1. The molar ratio of alcohol to R groups
attached to magnesium and aluminum was 1:1.
B. Polymerization of Ethylene
.... . _ _
The polymerization was done according to the
method of example 1-B, except that 2.0 ml of 0.600 M
triethylaluminum (1.20 mmoles) and an aliquot of catalyst
A prepared above containing 0.00585 mmoles of titanium
were used in a 2.8 liter reactor containing 1.6 liter
of dry, oxygen-free hexane. The ratio of cocatalyst
Al:Ti was 200:1. The dried reactor contents weighed
346 g. The melt index, I 2 J of the polyethylene was 5.4,
30,178A-F -15-
-16-
l~91~:Z
and the bull density of the powder was 24.3 lb/ft3
(0.389 g/cc). The catalyst efficiency was 1,232,000
g PE/g Ti.
COMPARATIVE EXPERIMENT A
a. Catalyst Preparation
A catalyst was prepared according to the
manner of example 2-A, except that no n-propyl alcohol
was used in the preparation of the catalyst. The
catalyst was prepared with the sequential addition of
25 mmoles of butylethylmagnesium, 12.5 mmoles triiso-
butylaluminum, 50 mmoles of ethylaluminum dichloride,
and a pre-mixed hexane solution containing 2.5 mmoles
of diethylzinc and 2.5 mmoles of tetraisopropoxytitanium.
The atomic ratios of Cl:Mg, Mg:Ti, and Zn:Ti were 4:1,
10:1, and 1:1, respectively.
b. Polymerization of Ethylene
Ethylene was polymerized in the manner of
example 2-B, except that 0.8 ml of 0.600 triethyl-
aluminum (0.48 mmoles) and an aliquot of catalyst ~A-a)
containing 0.0024 mmoles of titanium were used. The
atomic ratio of cocatalyst Al:Ti was 200:1. The dried
reactor contents weighed 59 grams. The melt index, I2,
of the polyethylene was 1.7, and the bulk density was
13.7 lb/ft3 (0.219 g/cc). The catalyst efficiency was
512,000 g PE/g Ti.
COMPARATIVE EXPERIMENT B
a. Catalyst Preparation
A catalyst was prepared according to the
method of example 2-A, except that no triisobutylaluminum
and no n-propyl alcohol were used. The catalyst was
prepared using the sequential addition of 25.0 mmoles
of butylethylmagnesium, 50 mmoles of ethylaluminum
30,178A-F -16-
~z~
dichloride, and a pre-mixed hexane solution containing
2.5 mmoles of diethylzinc and 2.5 mmoles of tetraiso-
propoxytitanium. The atomic ratios of Cl:Mg, Mg:Ti, and
Zn:Ti were 4:1, 10:1~ and 1:1, respectively.
b. Polymerization of Ethylene
Ethylene was polymerized according to the
manner of example 2-B, except that 1.2 ml of 0.600 M
triethylaluminum (0.72 mmoles) and an aliquot of catalyst
(B-a) containing 0.0035 mmoles of titanium were used.
The cocatalyst Al:Ti ratio was 205:1. The dried reactor
contents weighed 143 grams. Melt index, I2, of the
polyethylene was 1.60, and the bulk density of the
polyethylene powder was 14.2 lb/ft3 (0.227 g/cc). The
catalyst efficiency was 851,000 g PE/g Ti.
EXAMPLE 3
A. Catalyst Preparation
In the manner of example 1 A, a catalyst was
prepared by the sequential addition of 78.5 ml of 0.637
M butylethylmagnesium (50.0 mmoles) in hexane, 40.6 ml
of 0.616 M triisobutylaluminum (25.0 mmoles) in hexane,
14.5 ml of n-propyl alcohol (192.8 mmoles), and the
dropwise addition of 65.3 ml of 1.53 M ethylaluminum
dichloride (99.9 mmoles) in hexane. A white slurry
resulted after addition of ethylaluminum dichloride.
Then the total catalyst slurry was split into two equal
portions by volume, each containing 25 mmoles of magne-
sium. To one of the portions was added hexane solution
(mixed 2 hours ~7200 s) prior to use) containing 1.25
mmoles diethylzinc and 1.31 mmoles of tetraisopropoxy-
titanium. The final catalyst color changed to tan-brown.
The atomic ratios of Mg:Ti, Cl:Mg, and Zn:Ti were 19.1:1,
4:1, and 0.95:1, respectively. The molar ratio of alcohol
to alkyl groups attached to magnesium and aluminum was
1 . 10 : 1 .
30,178A-F -17-
-18-
12~9~.zz
B. Polymerization of Ethylene
Ethylene was polymerized according to the
manner of example 2-B using 2.2 ml of 0.921 M triethyl-
aluminum (2.026 mmoles) in hexane and an aliquot of
catalyst 3-A containing 0.0098 mmoles of titanium. The
cocatalyst Al:Ti ratio was 206:1. The dried reactor
contents weighed 473 grams. The melt index, I 2 of the
polyethylene was 10.8 and the bulk density of the
powder was 25.1 lb/ft3 (0.402 g/cc). Catalyst efficiency
was 1,008,000 g Pe/g Ti.
C. Polymerization of Ethylene
Ethylene was polymerized according to the
manner of example 2-B using 3.2 ml of 0.616 M triiso-
butylaluminum (1.971 mmoles) in hexane and an aliquot
of catalyst 3-A containing 0.00~8 mmoles titanium. The
cocatalyst Al:Ti ratio was 201:1. The dried reactor
contents weighed 425 grams. Melt index, I2, of the
polyethylene was 4.23, and the bulk density of the
powder was 24.1 lb/t3 (0.386 gag Catalyst efficiency
was 901,000 g PE/g Ti.
30,178A-F -18-
-19-
~9~ZZ
1. In the process for the polymerization of
one or more polymerizable ethylenically unsaturated
monomers containing one or more polymerizable ~=olefins
under Ziegler polymerization conditions wherein the
polymerization is conducted in the presence of a
transition metal-containing catalyst; the improvement
which comprises employing as the transition metal-
containing catalyst a catalytic product resulting from
(I) admixing in an inert hydrocarbon diluent and
in an atomsphere which excludes moisture and
oxygen
(A) at least one hydrocarbon soluble
organomagnesium materia;
(B) at least one organic alcoholic hydroxyl-
-containing material;
(C) at least one reducing halide source; and
(D) the reaction product or complex formed
by mixing at a temperature and/or a time
sufficient to provide a color change
(1) at least one transition metal (Tm)
compound having at least one
hydrocarbyloxy group attached to
said transition metal and
(2) at least one organozinc compound;
and wherein
30,1~8A F l
-20-
9~Z~
(a) the components are added in
the order (A), (B), (C) and
(D) or (A), (B), (D) and (C);
and
(b) the components are employed in
quantities so as to provide
- the following atomic ratios
Mg:Tm of 0.1:1 to 100:1; Zn:Tm
of 0.05:1 to 10:1; Cl:Mg of
2:1 to 20:1; and the OX:total
number of hydrocarbyl groups
attached to a metal atom in
component (A) is 0.1:5 to
1 . : 1 .
2. The process of Claim 1 wherein
(1) Component (A) is represented by the formula
R2Mg xMeR'x, wherein each R is independently
a hydrocarbyl group having from 1 to 20
carbon atoms; each R' is independently a
hydrogen, hydrocarbyl or hydrocarbyloxy group
having from 1 to 20 carbon atoms; Me is Al,
Zn or B; x has a value from zero to 10 and is
sufficient to render the organomagnesium
component hydrocarbon soluble; and x' has a
value equal to the valence of Me;
(2~ Component ~B) is represented by the formulas
R~0-R'~nOH and ~0-R'~nO-R")n, wherein each
R is a hydrocarbyl group having from 1 to 20
carbon atoms; each R' is independently a
divalent hydrocarbyl group having frGm 1 to
20 carbon atoms; each R" is independently
hydogen or a hydrocarbyl group having from 1
to 20 carbon atoms; at least one of which is
30,178A-F -20-
Z~
hydrogen; Z is a multivalent organic group
containing from 2 to 20 carbon atoms; n has a
value from zero to 10; and n' has a value of
from 2 to 10;
(3) Component (C) is represented by the formulas
Al(R3)3 mXm and B(R3)3 mXm including mixtures
thereof wherein each R3 is independently
hydrogen or a hydrocarbyl group as above
defined, X is a halogen, and m has a value
from 1 to 2;
(4) Component (D-1) is represented by the formula
Tm(OR'')nXz n or Tm(OR"~2O, wherein Tm is a
transition metal in its highest stable valence
state and being selected from groups IV-B,
V-B and VI-B of the Periodic Table of the
Elements; R" is a hydrocarbyl group hazing
from l to 20 carbon atoms; X is a halogen,
preferably chlorine or bromine; z has a value
corresponding to the valence of the transition
metal, Tm; n has a value of from one to the .
- valence state of the transition metal, Tm;
(5) Component (D-2) is represented by the formula
R2Zn and/ro RZnX wherein each R is independently
a hydrocarbyl group having from 1 Jo 20
carbon atoms and X is a halogen;
(6) the atomic ratio of Mg:Tm is 1:1 to 40:1;
(7) the atomic ratio of Zn:Tm is 0.1:1 to 5:1;
(8) the atomic ratio of Cl:Mg is 3:1 to 15:1; and
(9) the ratio of OH groups in component ~B):
total number of hydrocarbyl groups attached
to a metal atom in component (A) is 0.8:1 to
1.2:1.
30,178A-F -21-
