U.S. patent application number 11/786185 was filed with the patent office on 2007-08-23 for preparation of a magnesium halide support for olefin polymerization and a catalyst composition using the same.
This patent application is currently assigned to Formosa Plastics Corporation, U.S.A.. Invention is credited to Chih-Jian Chen, Gapgoung Kong, Zhongyang Liu, Honglan Lu.
Application Number | 20070197381 11/786185 |
Document ID | / |
Family ID | 32824634 |
Filed Date | 2007-08-23 |
United States Patent
Application |
20070197381 |
Kind Code |
A1 |
Lu; Honglan ; et
al. |
August 23, 2007 |
Preparation of a magnesium halide support for olefin polymerization
and a catalyst composition using the same
Abstract
A magnesium halide support material for a polyolefin catalysts
is disclosed. The magnesium halide of present invention is prepared
by reacting magnesium with an alkylhalide in a non-polar
hydrocarbon solvent. Preparation of the support does not require
the use electron donating solvents and therefore does not require
extensive washing to remove the solvent from the support.
Inventors: |
Lu; Honglan; (Port Lavaca,
TX) ; Kong; Gapgoung; (Sugarland, TX) ; Liu;
Zhongyang; (Port Lavaca, TX) ; Chen; Chih-Jian;
(Port Lavaca, TX) |
Correspondence
Address: |
HOWREY LLP
C/O IP DOCKETING DEPARTMENT
2941 FAIRVIEW PARK DRIVE, SUITE 200
FALLS CHURCH
VA
22042-7195
US
|
Assignee: |
Formosa Plastics Corporation,
U.S.A.
|
Family ID: |
32824634 |
Appl. No.: |
11/786185 |
Filed: |
April 11, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
10365558 |
Feb 12, 2003 |
7211534 |
|
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11786185 |
Apr 11, 2007 |
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Current U.S.
Class: |
502/439 |
Current CPC
Class: |
C08F 210/16 20130101;
C08F 10/02 20130101; C08F 10/02 20130101; C08F 10/02 20130101; B01J
27/138 20130101; C08F 210/16 20130101; C08F 10/02 20130101; C08F
10/00 20130101; C08F 10/02 20130101; C08F 4/651 20130101; C08F
4/6546 20130101; C08F 10/02 20130101; C08F 10/00 20130101; C08F
4/6543 20130101; C08F 210/14 20130101; C08F 4/6557 20130101; C08F
4/6555 20130101; C08F 2500/12 20130101; C08F 4/6548 20130101 |
Class at
Publication: |
502/439 |
International
Class: |
B01J 21/04 20060101
B01J021/04 |
Claims
1. A magnesium halide support for an olefin polymerization
catalyst, wherein the magnesium halide support is prepared by:
providing magnesium and an alkylhalide in a non-polar hydrocarbon
medium; providing a metal complex having the formula
M(OR).sub.nCl.sub.m to the non-polar hydrocarbon medium to initiate
a reaction between the magnesium and the alkylhaide, wherein M is
Zirconium or aluminum, n is from 1 to 4 and m is from 0 to 3, and R
is a hydrocarbon; and recovering the magnesium halide support.
2-6. (canceled)
7. A process for preparing a solid support for an olefin
polymerization catalyst comprising: combining magnesium and an
alkylhalide in a non-polar hydrocarbon medium; providing a metal
complex having the formula M(OR).sub.nX.sub.m to the non-polar
hydrocarbon medium to initiate a reaction between the magnesium and
the alkylhalide, wherein M is zirconium or aluminum, n is from 1 to
4, m is from 0 to 3, R is alkyl, X is halide; and recovering the
solid support.
8. The process for preparing a solid support of claim 7 wherein the
recovered solid support consists essentially of a mixed alkoxy
halide of magnesium and M.
9. The process for preparing a solid support of claim 7 wherein M
is zirconium and the metal complex is obtained by the reaction
between a zirconium halide represented by formula ZrX.sub.4 with an
alcohol represented by formula ROH; wherein the molar ratio of
alcohol to zirconium is about 1 to about 6, wherein R is alkyl, and
X is halide.
10. The process for preparing a solid support of claim 7 wherein
the metal complex is an aluminum alkoxide compound represented by
formula Al(OR).sub.3.
11. The process for preparing a solid support of claim 7 wherein
the molar ratio of metal complex to magnesium in the hydrocarbon
medium is about 0.01 to about 0.3.
12. The process for preparing a solid support of claim 7 wherein M
is zirconium and the molar ratio of alkylhalide to magnesium is
about 0.5 to about 3.0.
13. The process for preparing a solid support of claim 7 wherein M
is aluminum and the molar ratio of alkylhalide to magnesium is
about 1.0 to about 3.0.
Description
FIELD OF THE INVENTION
[0001] The present invention relates catalyst compositions useful
for olefin polymerization reactions, and more particularly to a
method of preparing a magnesium halide support from magnesium
powder and an alkylhalide using a non-polar solvent.
BACKGROUND OF THE INVENTION
[0002] Magnesium halide is a key component of titanium based
Ziegler-Natta catalysts which have been used extensively in the
polyolefin industry over the past 50 years. These catalysts are
typically composed of titanium incorporated onto the surface of a
magnesium halide support. It has been recognized that the catalyst
properties depend heavily on the chemical and physical properties
of magnesium halide support and the support properties influence
the morphology of the resulting polymer. Consequently, there has
been intense effort directed to preparing active magnesium halide
supports for olefin polymerization catalysts.
[0003] Most of the methods known in the art for preparing such
magnesium halide supports utilize various electron donating
solvents such as alcohol, ester, siloxy, and ether compounds. For
example, U.S. Pat. Nos. 4,987,212 and 4,642,328 discloses methods
involving the reaction of R.sub.2Mg solution with an alkylhalide in
a mixed solvent of ether and heptane. U.S. Pat. Nos. 5,091,353 and
5,192,732 describe a method wherein magnesium halide containing
aluminum is precipitated from an alcohol solution of magnesium
halide by the addition of alkylaluminum compounds to the solution.
In a method described in U.S. Pat. No. 4,302,566, THF is mixed with
magnesium halide and titanium halide compounds to make a solution
from which a solid catalyst component is prepared by
re-precipitation.
[0004] Method for preparing a magnesium halide support that utilize
electron donating solvents suffer the drawback that excessive
amounts of the electron donating solvent can intercalate into the
matrix of the support and `poison` the catalyst. As a result, it is
often necessary to extensively wash the matrix with non-polar
solvents or to treat the matrix with strong Lewis acids to remove
excessive electron donating solvent. These steps lengthen the
preparation process and themselves can potentially contaminate or
poison the catalyst.
[0005] U.S. Pat. No. 4,478,221 and European Patent No. 0 703 246 A1
describe a method that does not utilize an electron donating
solvent, wherein magnesium metal powder is reacted with
butylchloride in a non-polar solvent in the presence of
Ti(OR).sub.4 to initiate the reaction and then further treatment
with TiCl.sub.4/Ti(OR).sub.4/butylchloride results in a magnesium
halide supported catalyst. According to this method, the active
titanium catalyst is formed concomitantly with the precipitation of
the magnesium halide support. This makes it difficult to control
the homogeneity of the active site, therefore, polymers synthesized
using these catalysts display broad molecular distributions. Also,
the catalytic amount of Ti(OR).sub.4 used to initiate the reaction
between magnesium powder and butylchloride results in a tiny amount
of Ti(OR).sub.4-formed active site within the magnesium halide
support itself. This active site displays formidable activity and
competes with the desired active catalyst, producing heterogeneous
polymers. It is therefore difficult to employ a magnesium halide
support formed in this manner as a support for olefin
polymerization.
[0006] The reaction between magnesium and alkylhalide is seldom
successful without using titanium compounds such as TiCl.sub.4 or
Ti(OR).sub.4 to initiate the reaction. It would be beneficial to
develop a new method to initiate the reaction between magnesium and
alkyl halide without using titanium compounds.
[0007] U.S. Pat. No. 5,990,034 describes a method wherein a mixture
of alkylaluminum and alkylmagnesium is reacted with chlorosilane
containing a Si--H bond to produce a magnesium halide support
without using an ether solvent. However, alkylmagnesium compounds
are expensive, so this method for preparing a magnesium halide
support is not cost effective.
SUMMARY OF THE INVENTION
[0008] Accordingly, the present invention provides a magnesium
halide support for an olefin polymerization catalyst, wherein the
preparation of support does not require an electron donating
solvent. According to one embodiment, the support is prepared by
one aspect of the present invention is a catalyst composition for
olefin polymerization comprising a magnesium halide support and a
titanium catalyst component, wherein the magnesium halide support
is prepared by: [0009] providing magnesium and an alkylhalide in a
non-polar hydrocarbon medium, [0010] preparing a zirconium complex
by reacting a zirconium halide with an alcohol, [0011] providing
the zirconium complex to the non-polar hydrocarbon medium to
initiate a reaction between the magnesium and the alkylhalide, the
reaction yielding a magnesium halide support, and [0012] recovering
the magnesium halide support.
[0013] According to another embodiment, the magnesium halide
support is prepared by: [0014] providing magnesium and an
alkylhalide in a non-polar hydrocarbon medium, [0015] providing
aluminum alkoxide compound having the formula Al(OR).sub.3 wherein
R is a hydrocarbon to the non-polar hydrocarbon medium to initiate
a reaction between the magnesium and the alkylhalide, the reaction
yielding a magnesium halide support, and [0016] recovering the
magnesium halide support.
[0017] The solid magnesium halide support of the present invention
typically has the formula Mg.sub.pX.sub.q(OR).sub.rM.sub.s, where M
is Al or Zr, R is alkyl, X is halide, and p, q, r, and s are
numbers. Contact reaction between the support and a titanium
compound yields a titanium based catalysts.
[0018] A further aspect of the invention is a titanium-based
catalyst for olefin polymerization, wherein the catalyst utilizes a
magnesium halide support, as described above.
DETAILED DESCRIPTION
[0019] Generally, the reaction between magnesium and alkylhalide to
make an magnesium halide support has been performed in an electron
donating ether solvent such as tetrahydrofuran, diethylether, or
dibutylether. The reaction between magnesium powder and alkylhalide
is difficult to initiate without using these solvents.
[0020] The present invention provides a method wherein the reaction
between magnesium and an alkylhalide is initiated in the presence
of either a zirconium compound (A-1), which is obtained from the
reaction of zirconium halide with an alcohol, or in the presence of
an aluminum alkoxide Al(OR).sub.3, which is obtained from the
reaction between an alkylaluminum and an alcohol. Reaction between
magnesium and alkylhalide produces a magnesium halide support in a
non-polar aliphatic solvent such as hexane and heptane. This method
does not require the use of an electron donating solvent and is
also advantageous with regard to production cost because only small
amounts of (A-1) or Al(OR).sub.3 are required.
[0021] Initiation of the reaction between magnesium powder and an
alkyl halide in the presence of zirconium compound (A-1). Zirconium
compounds (A-1) are prepared by reacting a zirconium halide with an
alcohol. The resulting product (A-1) can be used directly, without
purification or characterization, to initiate the reaction of
magnesium with an alkylhalide. The reaction product (A-1) is
preferentially soluble in hydrocarbon solvents such as hexane or
heptane as described in reaction (1): ZrX.sub.4+n ROH+hydrocarbon
solvent ------->(A-1) Reaction (1)
[0022] Examples of suitable zirconium halides include zirconium
chloride, zirconium bromide, zirconium fluoride, and zirconium
iodide. Examples of suitable alcohols include aliphatic alcohols
having 2 to 14 carbon atoms such as n-butanol and 2-ethylhexanol.
The molar ratio of alcohol to zirconium can be from about 1 to
about 6. Generally, increasing the amount of alcohol relative to
the amount of zirconium increase the particle size of the resulting
magnesium halide support. Because the alcohol is employed as a
reagent and not as a solvent, extensive washing is not required to
remove the excess alcohol.
[0023] The reaction between magnesium and alkylhalide is initiated
in the presence of (A-1) in non-polar solvent such as hexane or
heptane. Once initiated, further reaction with alkylhalide results
in the formation of solid magnesium halide support, as shown in
reaction (2): Mg+RX+(A-1) ---->Magnesium halide
support[Mg.sub.pX.sub.q(OR).sub.rZr.sub.s] Reaction (2)
[0024] Magnesium is typically provided in the form of magnesium
powder. Examples of suitable alkylhalides include aliphatic halide
compounds represented by formula RX, where R is hydrocarbon having
2 to 14 carbon atom such as ethyl, propyl, butyl, pentyl, heptyl,
octyl, and X is halide. The molar ratio of alkylhalide to magnesium
in the reaction is typically about 0.5 to about 3.0 and the molar
ratio of zirconium to magnesium is typically about 0.01 to about
0.3.
[0025] The resulting magnesium halide support typically contains
about 1 to about 10% zirconium metal which is incorporated during
the initiation of the reaction between magnesium and alkylhalide.
The zirconium component that is incorporated into the resulting
magnesium halide does not catalyze olefin polymerization and
therefore does not contribute to heterogeneity of the resulting
polymer when the magnesium halide is used as a support material for
titanium based catalyst.
[0026] Initiation of the reaction between magnesium metal and
alkylhalide using (A-1) is typically carried out at a temperature
greater than about 50.degree. C. Once initiated, the reaction is
sustained by continuously feeding the reaction with alkylhalide and
a sufficient amount of (A-1) to keep the reaction going until all
the magnesium metal powder is consumed. After all the magnesium
powder has disappeared from the mixture, further reaction at about
40.degree. C. and 100.degree. C. for about 1 to about 4 hours
completes the reaction to form the magnesium halide support.
[0027] Initiation of the reaction between magnesium powder and an
alkylhalide in the presence of aluminum alkoxide. The reaction
between magnesium and alkylhalide can also be initiated in the
presence of aluminum alkoxide represented by formula Al(OR).sub.3,
where R is an aliphatic hydrocarbon. Suitable aluminum alkoxides
can be purchased or can be obtained by reacting the corresponding
alkylaluminum with an alcohol. As described in reaction (3), the
reaction between magnesium powder and alkylhalide in the presence
of Al(OR).sub.3 produces a magnesium halide support that likely has
the composition [Mg.sub.pX.sub.q(OR).sub.rAl.sub.s]. The reaction
is performed in non-polar solvent such as hexane and heptane at
elevated temperature. Mg(powder)+RCl+Al(OR).sub.3---->Magnesium
halide support[Mg.sub.pX.sub.q(OR).sub.rAl.sub.s] Reaction (3)
[0028] Suitable solvents for reaction (3) include hexane and
heptane. The molar ratio of alkylhalide to magnesium is typically
about 1.0 to about 3.0 and the molar ratio of Al(OR).sub.3 to
magnesium is typically about 0.01 to about 0.3.
[0029] The reaction between magnesium powder and alkylhalide is
initiated using a catalytic amount of Al(OR).sub.3 at a temperature
of about 60 to about 100.degree. C. Once initiated, the reaction is
sustained by continuously feeding the reaction with alkylhalide and
a sufficient amount of Al(OR).sub.3 to keep the reaction going
until all the magnesium powder in the mixture is consumed. Further
stirring at about 60 to about 100.degree. C. for about 1 to about 4
hours completes the reaction to form a magnesium halide
support.
[0030] This reaction produces granular type magnesium halide
supports having composition of [Mg.sub.pX.sub.q(OR).sub.rM.sub.s]
with an average particle size of about 15 to about 75 .mu.m. The
particle size can be adjusted by varying the alkoxide group and/or
the reaction temperature. This method for preparing a magnesium
halide support is very advantageous in terms of manufacturing cost
because it does not involve any electron donating solvent and
therefore does not require extensive washing to remove intercalated
solvent.
[0031] Highly active catalysts can be prepared by contact reaction
between the above described magnesium halide supports and titanium
halide compounds represented by formula TiL.sub.nX.sub.4-n, where L
is non-halide ligand and X is halide. Such a contact reaction can
be carried out in a hydrocarbon solvent. For example, titanium
alkoxy halide compounds represented by formula
Ti(OR).sub.4-nX.sub.n or titanium amide halide compounds
represented by Ti(NR.sub.2).sub.4-nX.sub.n, wherein R is alkyl, X
is halide, and n is number less than 4, can be reacted with the
magnesium halide support in hydrocarbon solvent to incorporate a
titanium active center into the support, providing a highly active
catalyst. Alternatively, organometallic titanium compounds
containing a .pi.-ligand such as cyclopentadienyl or a derivatives
of a cyclopentadienyl ligand such as indene, fluorine, or a
chelating amide ligand such as carbodiimide or .beta.-ketimidate
can be reacted with the magnesium halide support to provide a
corresponding catalyst. Upon incorporation of a proper titanium
component, the magnesium halide support prepared according to the
present invention can be used as a titanium catalyst for olefin
polymerization, e.g., polyethylene and polypropylene.
[0032] Preparation of a highly active catalyst for ethylene
polymerization. A highly active catalyst composition can be
prepared by reacting the magnesium halide support prepared above
with titanium halide compounds, represented by formula
Ti(OR).sub.4-nX.sub.n where X is a halide, R is an alkyl group, and
n is number less than 4. The magnesium halide support and titanium
halide compounds are reacted such that Ti/Mg atomic ratio is in the
range of about 0.01 to about 2.0, more typically about 0.1 to about
1.0. The contact reaction is carried out in a hydrocarbon medium at
a temperature of about 20 to about 100.degree. C. for about 1 to
about 6 hours. Examples of suitable titanium compounds include
titanium tetrahalides such as TiCl.sub.4, TiBr.sub.4, TiI.sub.4,
alkoxy titanium halides such as Ti(OCH.sub.3)Cl.sub.3,
Ti(OC.sub.2H.sub.5)Cl.sub.3, Ti(OC.sub.4H.sub.9)Cl.sub.3,
Ti(OC.sub.8H.sub.17)Cl.sub.3, Ti(OCH.sub.3).sub.2Cl.sub.2,
Ti(OC.sub.2H.sub.5).sub.2Cl.sub.2,
Ti(OC.sub.4H.sub.9).sub.2Cl.sub.2,
Ti(OC.sub.8H.sub.17).sub.2Cl.sub.2, and tetraalkoxy titaniums such
as Ti(OCH.sub.3).sub.4, Ti(OC.sub.2H.sub.5).sub.4,
Ti(OC.sub.4H.sub.9).sub.4.
[0033] Preparation of a high performance catalyst for ethylene
co-polymerization. The magnesium halide support described above can
be utilized to make a high performance catalyst for producing
ethylene co-polymer having narrow molecular weight distribution and
homogeneous compositional distribution. According to one
embodiment, a high performance catalyst is prepared by:
[0034] treating the magnesium halide support with aluminum
compounds obtained from the reaction of R.sub.3Al with an amine or
an alcohol;
[0035] contact reaction between the support and a titanium halide
compound represented by formula Ti(OR).sub.4-nX.sub.n to produce a
titanium-containing precursor catalyst, where R is alkyl and X is
halide; and
[0036] treatment of the precursor catalyst with mixture of an
alkylmagnesium compound and an aluminum compounds obtained from the
reaction of R.sub.3Al with an amine or an alcohol.
[0037] Suitable aluminum compounds are prepared by reacting
R.sub.3Al with a secondary alkylamine. The reaction can be carried
out at room temperature for about 1 to about 3 hours. Treatment of
the magnesium halide support with the aluminum compound is carried
out such that Al/Mg atomic ratio is about 0.05 to about 1.0 and the
temperature is preferably about 20 to about 80.degree. C. in a
non-polar solvent such as hexane or heptane. Examples of suitable
compounds having the formula R.sub.3Al include Me.sub.3Al,
Et.sub.3Al, (iBu).sub.3Al, and (C.sub.8H.sub.17).sub.3Al.
[0038] After the magnesium halide support has been treated with the
aluminum compound, it is contacted with a titanium alkoxyhalide
compound having formula Ti(OR').sub.4-nX.sub.n, e.g.,
Ti(OCH.sub.3)Cl.sub.3, Ti(OC.sub.2H.sub.5)Cl.sub.3,
Ti(OC.sub.4H.sub.9)Cl.sub.3, Ti(OC.sub.8H.sub.17)Cl.sub.3,
Ti(OCH.sub.3).sub.2Cl.sub.2, or Ti(OC.sub.2H.sub.5).sub.2Cl.sub.2,
to obtain a solid catalyst precursor containing titanium and
magnesium halide. Contact reaction between the aluminum-treated
support and the titanium halide is typically carried out such that
the Ti/Mg atomic ratio is about 0.1 to about 2.0 and the reaction
temperature is about 10 to about 60.degree. C. for 1 to 4 hours in
a non-polar solvent such as hexane or heptane.
[0039] The catalyst precursor is further treated with a mixture of
dialkylmagnesium and the aluminum compound, wherein the amount of
dialkylmagnesium is such that there is about 1 mmol of magnesium
per gram of solid precursor catalyst. The reaction temperature is
typically about 10 to about 60.degree. C. in a non-polar solvent
such as hexane or heptane.
[0040] Catalysts prepared as described above are capable of
producing polymers having narrow molecular weight distributions and
narrow compositional distributions. These catalyst compositions can
be activated with ordinary alkylaluminum compounds as a
co-catalyst. The alkylaluminum compounds are used in an amount that
is effective to promote the catalytic activities of the solid
catalyst component. Typically, the amount of alkylaluminum is
sufficient to provide an aluminum to titanium molar ratio of about
2 to about 500, more typically about 2 to about 100, and most
typically about 2 to about 30. Examples of suitable alkylaluminum
compounds include trialkylaluminums such as triethylaluminum,
tributylaluminum, trioctylaluminum, trimethylaluminum;
dialkylaluminum halides such as diethylaluminum chloride and
dibutylaluminum chloride; and alkylaluminum sesquichlorides such as
ethylaluminum sesquichloride and butylaluminm sesquichloride.
[0041] One measure of molecular weight distribution for is melt
flow ratio (MFR), which is the ratio of the high load melt index
(HLMI or I.sub.21.6) to the melt index (M.I. or I.sub.2.16) of a
given resin, that is: MFR=HLMI/M.I.
[0042] For a regular resins, MFR values tends to increase as M.I.
decreases and MFR values tends to decrease as M.I. increases. The
melt flow ratio is believed to be an indication of the molecular
weight distribution of the polymer and the higher the value, the
broader the molecular weight distribution. Resins having relatively
low MFR values for a given melt index M.I. typically have
relatively narrow molecular weight distributions. Generally, resins
having relatively low MFR values produce films of better strength
properties than resins with high MFR values.
[0043] The average particle size (APS) and bulk density (B/D) of
the support are two parameters that are related to the morphology
of the support and which are important in the polymerization
process. It is within the ability of one of skill in the art to
decide the optimum APS and B/D for a support depending on their
intended application.
[0044] The following examples are included to demonstrate
particular embodiments of the invention. It should be appreciated
by those of skill in the art that the techniques disclosed in the
examples which follow represent techniques discovered by the
inventor to function well in the practice of the invention, and
thus can be considered to constitute some of the preferred modes
for its practice. However, those of skill in the art should, in
light of the present disclosure, appreciate that many changes can
be made in the specific embodiments which are disclosed and still
obtain a like or similar result without departing from the spirit
and scope of the invention.
EXAMPLE 1
[0045] Preparation of magnesium halide support. ZrCl.sub.4 (30
mmol) was mixed with 100 mL hexane and reacted with 120 mmol of
2-ethylhexanol at room temperature for 1 hour to yield a pale brown
solution (A-1). Magnesium powder (132 mmol), 10 mL butylchloride,
400 mL hexane, and 0.23 g of iodine were introduced successively
into 1-liter glass flask. An amount of zirconium solution (A-1)
sufficient to provide 6 mmol of zirconium was added to the mixture.
The mixture was heated to 60.degree. C. for 1 hour to initiate the
reaction. n-Butylchloride (15 mL) was added slowly over 4 hours.
When the addition was complete, the reaction mixture was stirred at
70.degree. C. for 2 additional hours and then cooled to room
temperature (20.degree. C.). The resulting precipitate was washed
three times with hexane to yield granule type solid magnesium
halide support having an average particle size of 50 .mu.m.
[0046] Preparation of highly active catalyst. A hexane solution of
triethylaluminum (100 mmol) was placed in 200 mL flask and 200 mmol
of dicyclohexylamine was added slowly over 30 minutes followed by
stirring for 1 hour to yield a pale yellow aluminum solution
(B-1).
[0047] Magnesium halide support (3.0 g), as prepared above, was
placed in a 500 mL flask with 150 mL hexane and 6 mmol of aluminum
solution (B-1) was added. After 6 hour stirring at room temperature
the liquid portion was decanted and the solid was washed with 200
mL hexane. 2-Ethylhexoxytitanium trichloride (15 mmol) and 150 mL
hexane was added and the resulting slurry was stirred for 1 hour at
room temperature. The liquid portion was decanted and the solid was
washed with 500 mL hexane. Analysis results shows it contains 3.9%
Ti, 18% Mg, and 3.0% Zr.
[0048] Ethylene polymerization. A 2.0 liter autoclave reactor was
purged with nitrogen and charged with 1000 mL of purified hexane.
The temperature was raised to 65.degree. C. and 2.0 mmol of
(n-C.sub.8H.sub.17).sub.3Al with 0.05 g of catalyst were injected.
The autoclave was pressurized 16 psi with hydrogen, and ethylene
was introduced to maintain total pressure at 90 psi. Polymerization
was carried out at 85.degree. C. for 1 hour. The resulting polymer
suspension was filtered and dried. Polymerization results are
summarized in Table 1.
EXAMPLES 2-4
[0049] A catalyst was prepared as described in Example 1 except
that the amount of (A-1) was varied to provide the amount of
zirconium listed below. Polymerization was carried out as described
in Example 1 and results are listed in Table 1. TABLE-US-00001
Example Zr amount Average Particle size (.mu.m) 2 3 mmol 75 3 12
mmol 40 4 25 mmol 30
EXAMPLE 5-8
[0050] Catalyst was prepared as described in Example 1 except that
the alcohols listed below were used in place of 120 mmol of
2-ethylhexanol. Polymerization was carried out in the same way as
in Example 1 and results are listed in Table 1. TABLE-US-00002
Examples Alcohol Amount 5 2-ethylhexanol 120 mmol 6
i-butanol/2-ethylhexanol 60 mmol/60 mmol 7
i-propanol/2-ethylhexanol 60 mmol/60 mmol 8 2-ethylhexanol 60
mmol
EXAMPLE 9
[0051] Preparation of magnesium halide support. Magnesium powder
(3.2 g), 400 mL hexane, and 0.23 g of iodine were introduced
successively into a 1-liter glass flask. The mixture was stirred
and heated at 80.degree. C. When the temperature reached 80.degree.
C., 6.73 mmol of Al[O--CH(CH.sub.3)C.sub.2H.sub.5].sub.3 was
introduced rapidly, followed by the slow addition of 30 mL of
n-C.sub.4H.sub.9Cl over 4 hours, followed by further stirring at
80.degree. C. for 2 additional hours. The mixture was cooled to
room temperature (20.degree. C.) and the resulting precipitate was
washed three times with hexane to yield the solid magnesium halide
support.
[0052] Highly active catalyst preparation. Triethylaluminum (100
mmol) was placed in 200 mL flask and 200 mmol of dicyclohexylamine
was added slowly over 30 minutes and stirred for 1 hour to yield
pale yellow aluminum solution (B-1).
[0053] Magnesium halide support (3.0 g), as prepared above, was
placed in a 500 mL flask with 150 mL hexane and 6 mmol of aluminum
solution (B-1). After stirring for 6 hour at room temperature, the
liquid portion was decanted and the solid was washed with 200 mL
hexane. Then, 15 mmol of 2-ethylhexoxytitanium trichloride and 150
mL hexane was added and the slurry was stirred for 1 hour at room
temperature. The liquid portion was decanted and the solid was
washed with 500 mL hexane. The resulting catalyst contained 4.2%
Ti.
[0054] Ethylene polymerization. Polymerization was carried out in
the same way as in Example 1 and results are listed in Table 1.
EXAMPLE 10-12
[0055] Preparation of magnesium halide support. For each replicant,
triethylaluminum (40 mL of 1 M solution) was placed in 500 mL flask
and diluted with 60 mL hexane. Slowly, 40 mmol of 2-ethylhexanol
was added at 0.degree. C. and consecutively 80 mmol of the alcohols
listed below was added slowly at 0.degree. C. to prepare aluminum
alkoxy-compounds (A-2). TABLE-US-00003 Example Alcohol 10 i-butanol
11 ethanol 12 i-propanol
[0056] The magnesium halide support was prepared in the same way as
in Example 9 except that 5 mmol of aluminum alkoxy compounds (A-2)
prepared above were used in place of
Al[O--CH(CH.sub.3)C.sub.2H.sub.5].sub.3.
[0057] Catalysts were prepared in the same way as in Example 9,
followed by ethylene polymerization that was carried out in the
same way as in Example 1. The polymerization results are listed in
Table 1.
EXAMPLE 13
[0058] Preparation of high performance catalyst. Magnesium halide
support was prepared in the same way as in Example 1.
Triethylaluminum (100 mmol) was placed in 200 mL flask and 200 mmol
of dicyclohexylamine was added slowly over 30 minutes, and stirred
for 1 hour to make pale yellow aluminum solution (B-1).
Dibutylmagnesium solution (20 mmol) in heptane and 40 mmol of
aluminum solution (B-1) were mixed to form a clear solution.
Without further separation or purification, this hexane solution
was used as (B-2) solution.
[0059] Magnesium halide support (3.0 g), prepared as described
above, was placed in 500 mL flask with 150 mL hexane 6 mmol of
aluminum solution (B-1). After 6 hours stirring at room
temperature, the liquid portion was decanted and the solid was
washed with 200 mL hexane. 2-Ethylhexoxytitanium trichloride (15
mmol) was added with 150 mL hexane and the slurry was stirred for 1
hour at room temperature. The solution part was decanted and washed
with 500 mL hexane. After make-up of hexane up to 150 mL, 3.0 mmol
magnesium-amide complex (B-2) was added and the mixture was stirred
at 40.degree. C. for 3 hours to make a catalyst. Analysis results
shows the catalyst contains 3.9% Ti and 19.1% Mg.
[0060] Ethylene polymerization. A 2.0 liter autoclave reactor was
purged with nitrogen and charged with 1000 mL of purified hexane.
The temperature was brought to 65.degree. C. and 2.0 mmol of
(n-C.sub.8H.sub.17).sub.3Al with 0.05 g of catalyst, as prepared
above, were injected. The autoclave was pressurized with hydrogen
and total pressure was brought to 6.0 kg/cm.sup.2-G with ethylene.
The polymerization was carried out at 85.degree. C. for 1 hour.
After polymerization, the polymer suspension was filtered and
polymer was dried to yield 160 g of polymer, having M.I. of 1.2 and
MFR (21.6/2.16 kg/min) of 25.0, indicating a narrow molecular
weight distribution.
[0061] Ethylene/1-hexene co-polymerization. A 2.0 liter autoclave
reactor was purged with nitrogen and charged with 1000 mL of
purified hexane. 1-Hexene (60 mL) was injected and the temperature
was brought to 65.degree. C. (n-C.sub.8H.sub.17).sub.3Al (2.0 mmol)
with 0.05 g of catalyst, as prepared above, were injected and the
autoclave was pressurized with hydrogen and total pressure was
brought to 6.0 kg/cm.sup.2-G with ethylene. The polymerization was
carried out at 85.degree. C. for 30 min. After polymerization,
methanol was added to quench the reaction and the polymer
suspension was filtered and dried to yield 105 g of ethylene
co-polymer having M.I. of 1.5, MFR (21.6/2.16 kg) of 24.2, Tm of
123.5.degree. C., and a density of 0.925. These data indicate that
the polymer has a narrow molecular weight distribution and
compositional distribution.
EXAMPLE 14 (COMPARATIVE EXAMPLE)
[0062] Attempted preparation of catalyst in the absence of
initiator or electron-donating solvent. Magnesium powder (3.2 g),
10 mL butylchloride, 400 mL hexane, and 0.23 g of iodine were
introduced successively into 1-liter glass flask and the mixture
was heated to 85.degree. C. to in an attempt to initiate the
reaction between the magnesium metal and the alkylhalide. After
continued stirring for 3 hours, the reaction was not initiated and
all of the magnesium powder remained unreacted. The catalyst could
not be prepared and polymerization could not be carried out.
EXAMPLE 15 (COMPARATIVE EXAMPLE)
[0063] Preparation of magnesium halide support. A magnesium halide
support was prepared according to U.S. Pat. No. 4,511,703.
Dibutylmagnesium solution (500 mL of 1.0 M) in heptane and 50 mL of
di-isoamyl ether were placed in a 1-liter glass reactor and the
temperature was brought to 50.degree. C. Over the span of 2 hours,
115 mL of t-butylchloride were added, dropwise. Following the
addition, the suspension was reacted for 2 hours at 50.degree. C.
and the resulting precipitate was washed five times at 50.degree.
C. with 500 mL n-hexane. Even following the repeated washings, the
magnesium halide support contains isoamyl ether.
[0064] Catalyst preparation. Triethylaluminum (100 mmol) was placed
in a 200 mL flask and 200 mmol of dicyclohexylamine was added
slowly over 30 minutes. The mixture was stirred for 1 hour to yield
a pale yellow aluminum solution (B-1).
[0065] Magnesium halide support (3.0 g), as prepared above, was
placed in a 500 mL flask with 150 mL hexane and 6 mmol of aluminum
solution (B-1). After 6 hour stirring at room temperature, the
liquid portion was decanted and the solid was washed with 200 mL
hexane. 2-Ethylhexoxytitanium trichloride (15 mmol) was added with
150 mL hexane and the slurry was stirred for1 hour at room
temperature. The liquid portion was decanted and the remaining
solid was washed with 500 mL hexane.
[0066] Ethylene polymerization. Polymerization was carried out as
described in Example 1, but activity was much lower than the
catalyst of Example 1, as listed in Table 1.
EXAMPLE 16 (COMPARATIVE EXAMPLE)
[0067] Reaction of magnesium and butylchloride in the presence of
Ti(OnPr).sub.4. Magnesium powder (3.2 g), 400 mL hexane, and 0.43 g
of iodine were introduced successively into 1-liter glass flask,
and 0.7 g of Ti(OnPr).sub.4 and 0.3 mL BuCl were added. The mixture
was heated to 85.degree. C. to initiate the reaction and then the
temperature was lowered to 80.degree. C. At this temperature 30 mL
of n-butylchloride was added over 3 hours. The resulting mixture
was stirred for and additional 2 hours at 80.degree. C. and then
cooled to room temperature (20.degree. C.). The solid precipitate
was washed with hexane three times to yield the catalyst
component.
[0068] Polymerization was carried out in the same way as in Example
1 and the magnesium halide support prepared above by itself shows
substantial activity producing broad molecular weight distribution
(MFR=34). Because this support itself is quite catalytically
active, it is not suitable as a magnesium halide support for
catalysts.
EXAMPLE 17 (COMPARATIVE EXAMPLE)
[0069] A catalyst was prepared according to U.S. Pat. No.
4,748,221. Magnesium powder (3.2 g), 400 mL hexane, and 0.43 g of
iodine were introduced successively into 1-liter glass flask and
the mixture was brought to 80.degree. C. When temperature reached
80.degree. C., 3.3 g of titanium tetrachloride and 5.0 g of
Ti(OnPr).sub.4 were added, followed by the slow addition over 4
hours of 30 mL of n-butylchloride. The reaction mixture was stirred
for an additional 2 hours at 80.degree. C. and then cooled to room
temperature (20.degree. C.). The solid precipitate was washed with
hexane three times to obtain a catalyst component
[0070] Ethylene and ethylene/1-hexene polymerization.
Polymerization was carried out as described in Example 13. Ethylene
homo-polymerization produced 106 g polymer with a M.I. of 1.1 and
MFR (21.6/2.16 kg) of 32.0, indicating much broader molecular
weight distribution than the present invention.
[0071] Ethylene/1-hexene polymerization, which was carried out in
the same way as in Example 13, produced 62 g ethylene co-polymer
having a M.I. of 1.2, MFR (21.6/2.16 kg) of 30.2, Tm of
126.5.degree. C., and density of 0.940. This density is much than
that of the polymer produced using the catalyst of Example 13.
TABLE-US-00004 TABLE 1 Example Yield (g) APS(*) (.mu.m) B/D(*) M.I.
1 270 700 0.35 2.0 2 280 780 0.33 1.6 3 260 500 0.32 2.3 4 290 350
0.36 2.5 5 260 650 0.30 1.8 6 280 660 0.32 1.5 7 260 680 0.33 1.4 8
290 670 0.35 1.6 9 280 460 0.29 1.7 10 270 370 0.35 1.2 11 250 350
0.32 1.3 12 300 480 0.32 1.1 13 160 500 0.35 1.2 14 0 -- -- -- 15
60 450 0.38 0.5 16 120 300 0.26 1.1 17 156 650 0.31 1.6
[0072] In light of the present disclosure, one of skill in the art
will appreciate that one aspect of the present invention is a
magnesium halide support for an olefin polymerization catalyst,
wherein the magnesium halide support is prepared by providing
magnesium and an alkylhalide in a non-polar hydrocarbon medium;
providing a metal complex having the formula M(OR).sub.nCl.sub.m to
the non-polar hydrocarbon medium to initiate a reaction between the
magnesium and the alkylhalide, wherein M is zirconium or aluminum,
n is from 1 to 4 and m is from 0 to 4, and R is hydrocarbon; and
recovering the magnesium halide support. Typically, when M is
zirconium, n is from 1 to 4 and m is from 0 to 3. Typically, when M
is aluminum, n is from 1 to 3 and m is from 0 to 2.
[0073] A further aspect of the invention is a method of preparing a
magnesium halide support for an olefin polymerization catalyst, the
method comprising: providing magnesium and an alkylhalide in a
non-polar hydrocarbon medium; preparing a zirconium complex by
reacting a zirconium halide with an alcohol; providing the
zirconium complex to the non-polar hydrocarbon medium to initiate a
reaction between the magnesium and the alkylhalide, the reaction
yielding a magnesium halide support; and recovering the magnesium
halide support. According to one embodiment, the magnesium halide
support has the formula Mg.sub.pX.sub.q(OR).sub.rZr.sub.s where R
is alkyl, X is halide, and p, q, r, and s are numbers. According to
one embodiment the zirconium halide is reacted with an alcohol such
that the ratio of alcohol to zirconium is about 1 to about 6.
According to one embodiment, the ratio of alkylhalide to magnesium
in the hydrocarbon medium is about 0.5 to about 3. According to one
embodiment, the ratio of zirconium to magnesium in the hydrocarbon
medium is about 0.01 to about 1.0. According to one embodiment, the
alkylhalide has the formula RX, wherein R is a branched or
unbranched hydrocarbon having 2 to 14 carbon atoms, and X is a
halide. According to one embodiment, R is selected from the group
consisting of ethyl, propyl, butyl, pentyl, heptyl, and octyl.
According to one embodiment, after the reaction is between
magnesium and alkylhalide is initiated, additional alkylhalide is
provided to the non-polar hydrocarbon medium in an amount
sufficient to sustain the reaction until essentially all of the
magnesium is consumed. According to one embodiment, the reaction
between magnesium and alkylhalide is initiated at a temperature
greater than about 50.degree. C.
[0074] A still further aspect of the invention is a method of
preparing a magnesium halide support for an olefin polymerization
catalyst, the method comprising: providing magnesium and an
alkylhalide in a non-polar hydrocarbon medium, providing aluminum
alkoxide compound having the formula Al(OR).sub.3 wherein R is a
hydrocarbon to the non-polar hydrocarbon medium to initiate a
reaction between the magnesium and the alkylhalide, the reaction
yielding a magnesium halide support, and recovering the magnesium
halide support.
[0075] All of the compositions and methods disclosed and claimed
herein can be made and executed without undue experimentation in
light of the present disclosure. While the compositions and methods
of this invention have been described in terms of preferred
embodiments, it will be apparent to those of skill in the art that
variations may be applied to the compositions and methods and in
the steps or in the sequence of steps of the method described
herein without departing from the concept, spirit and scope of the
invention. More specifically, it will be apparent that certain
agents which are chemically related may be substituted for the
agents described herein while the same or similar results would be
achieved. All such similar substitutes and modifications apparent
to those skilled in the art are deemed to be within the spirit,
scope and concept of the invention as defined by the appended
claims.
* * * * *