U.S. patent application number 09/761151 was filed with the patent office on 2002-09-05 for constrained geometry ligands and complexes derived therefrom.
Invention is credited to Gately, Daniel A., Sullivan, Jeffrey M..
Application Number | 20020123639 09/761151 |
Document ID | / |
Family ID | 25061319 |
Filed Date | 2002-09-05 |
United States Patent
Application |
20020123639 |
Kind Code |
A1 |
Sullivan, Jeffrey M. ; et
al. |
September 5, 2002 |
Constrained geometry ligands and complexes derived therefrom
Abstract
A novel constrained geometry titanium(II) diene complex and
ligands of such complexes are described. The novel complex has an
olefin polymerization activity substantially in excess of a defined
activity standard characteristic of analogous prior art constrained
geometry diene complexes. Methods for the synthesis of the novel,
high-activity complexes are described.
Inventors: |
Sullivan, Jeffrey M.;
(Loveland, CO) ; Gately, Daniel A.; (Berthoud,
CO) |
Correspondence
Address: |
Edward S. Irons
3945 - 52nd Street, N. W.
Washington
DC
20016
US
|
Family ID: |
25061319 |
Appl. No.: |
09/761151 |
Filed: |
January 17, 2001 |
Current U.S.
Class: |
556/52 ;
526/183 |
Current CPC
Class: |
C07F 17/00 20130101;
Y10S 526/943 20130101 |
Class at
Publication: |
556/52 ;
526/183 |
International
Class: |
C08F 004/44; C07F
017/00 |
Claims
We claim:
1. A compound having the formula 10wherein said compound has an
olefin polymerization activity substantially in excess of loot of
standard activity.
2. The compound of claim 1 wherein the olefin polymerization
activity of said compound is at least 130% of said standard
activity.
3. The compound of claim 1 wherein the olefin polymerization
activity of said compound is at least 150% of said standard
activity.
4. A method for preparing a compound of claim 1 which comprises:
(i) providing a first reactor containing the reaction product of a
cyclopentadienyl silyl amine and an alkali metal alkyl, (ii)
providing a second reactor containing the adduct of formula
MX.sub.4.DME wherein M is a group 4 element, X is a halogen, and
DHE is dimethoxyethane, (iii) adjusting the pot temperature of each
of said first reactor and said second reactor to be within the
ranges of about 20.degree. C.-30.degree. C., (iv) thereafter
combining the contents of the first reactor with the contents of
the second reactor wherein a reaction mixture is produced in said
second reactor, and wherein said reaction mixture produced in said
second reactor contains a compound of the formula 11(v) distilling
solvents from said reaction mixture containing said compound in
said second reactor, (vi) converting said step (iv) compound to a
compound as set forth in claim 1, and wherein said compound as set
forth in claim 1 produced in step (iv) has olefin polymerization
activity substantially in excess of 100% of the standard
activity.
5. A ligand of a compound of claim 1 wherein said ligand has the
formula: 12wherein X is a halogen and R is a C.sub.1 to C.sub.10
alkyl group.
6. The ligand of claim 5 wherein X is chlorine and R is t-butyl.
Description
FIELD OF THE INVENTTON
[0001] This invention relates to constrained geometry complexes of
group 4 metals and dienes characterized by high olefin
polymerization activity, to ligands of such complexes and to
methods for the production of such complexes and ligands.
BACKGROUND OF THE INVENTION
[0002] U.S. Pat. No. 5,470,993 describes the synthesis of
constrained ; geometry group 4 metal diene complexes by contacting
a reduced form of a group 4 metal tetrahalide, a diene and an
appropriate dianion ligand of the desired metal complex.
[0003] The diene complexes may have the formula which appears at
lines 20-34 of Column 5 of U.S. Pat. No. 6,015,916 as follows:
1
[0004] The corresponding dihalo ligand may have the formula also
set forth in U.S. Pat. No. 6,015,916 (see Formula II of claim 1):
2
[0005] The ligand may be any corresponding dihalo compound in which
the chlorine substituents are replaced by bromine, iodine or
fluorine and in which the "t-bu" substituent is replaced by any
alkyl group.
[0006] U.S. Pat. No. 6,015/916 describes the synthesis of similar
complexes by treatment of a dihalo ligand of a metallocene compound
with an alkali metal alkyl and a diene. The specification of U.S.
Pat. No. 6,015,916 is, by express reference, incorporated herein
and made a part of this specification.
[0007] German Application DE 197 39 946 A1 describes a metallocene
synthesis in which an appropriate ligand is converted to a
metallocene by treatment with an adduct of Formula (I)
M.sup.1X.sub.nD.sub.a
[0008] in which M.sup.1 denotes a metal of groups 3, 4, 5 or 6 of
the periodic system of elements (PSB) or an element of the group of
lanthanides or actinides, preferably titanium, zirconium, or
hafnium, by special preference zirconium; X is the same or
different, being halogen, a C.sub.1-10-alkoxy, C.sub.6-10-aryloxy,
C.sub.1-10-alkylsulfonate such as mesylate, triflate, nonaflate, a
C.sub.6-10arylsulfonate such as tosylate, benzene sulfonate, a
C.sub.1-10-alkylcarboxylate such as acetate, formate, oxalate, or a
1,3-dicarbonylate such as acetylacetonate or a fluorinated
1,3-dicarbonylate; n is an integer and equals 2, 3, 4, 5 or 6 and
corresponds to the oxidation number of the metal M.sup.1; a is an
integer or a fraction number and 0<a.ltoreq.4; and D is a
linear, cyclic, or branched oligoether or polyether containing at
least two oxygen atoms or an oligoether or polyether containing at
least two sulfur atoms.
[0009] There is a need for group 4(II) diene complexes of high
catalytic activity in which these disadvantages are reduced or
eliminated and for dihalo ligands of such complexes.
[0010] Accordingly, it is an object of this invention to provide
novel cyclopentadienyl group 4 metal diene complexes and dihalo
ligands or such complexes which provide uniquely active olefin
polymerization catalysts.
[0011] It is a related object of the invention to provide
cyclopentadienyl group 4 metal diene complex single site
polymerization catalysts and catalyst compositions of low impurity
content such that the single site functionality thereof is not
significantly impaired.
[0012] It is a specific object of the invention to provide a
magnesium-free cyclopentadienyl group 4 metal diene complex
metallocene.
Definitions
[0013] The following expressions have the meaning set forth:
[0014] (1) Cyclopentadienyl group means cyclopentadienyl,
tetraalkylcyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl,
tetrahydrofluorenyl, or octahydrofluorenyl.
[0015] (2) The expressions group 4(II) and group 4(III) mean a is;
group 4 metal of valence 2(II) or 3(III).
[0016] (3) A Group 4(II) metallocene compound is a compound
comprised of a group 4(II) metal bonded to one or more
cyclopontadienyl groups.
[0017] (4) A Group 4(II) metallocene ligand is a chemical precursor
which contains a cyclopentadienyl or substituted cyclopentadienyl
group from which a group 4(II) metallocene may a synthesized.
[0018] (5) Constrained geometry compound or catalyst (CGC) means a
catalyst in which the metal conter is contained in a ring structure
and covalently bonded to a cyclic group via a delocalized n-system
and covalently bonded via a sigma-bond to another atom, e.g.,
carbon, nitrogen, oxygen. A small ring size induces constraint
about the metal atom center. For titanium-containing CGCs, the
incorporated titanium atom can be in the +4, +3, or +2 formal
oxidation state. See EP application 90309496.9, WO 95/00526 and
U.S. Pat. No. 5,470,993.
[0019] (6) CpSA ligand means (t-butylamino)
(tetramethylcyclopentadienyl) dimethylsilane.
[0020] (7) (CpSA) means doubly-deprotonated CpSA ligand.
[0021] (8) (CpSA)2-TiCl.sub.2 means [(t-butylamido)
(tetramethylcyclopentadienyl) dimethylsilan]titanium
dichloride.
[0022] (9) Activity means generally the quantity of polymer
produced under standard conditions by a defined amount of catalyst
per unit time.
Catalytic Activity Determination
[0023] As used in this application, catalyst efficiency or activity
is based on ethylene consumption in a batch reactor under standard
conditions for temperature, solvent, monomer quantities, hydrogen
quantities, monomer pressure and run time.
[0024] The activity of the sample catalyst is reported as the
percentage of activity of the sample versus the activity of a
standard ("standard activity"). For purposes of this application,
the "standard" is the CGC group 4(II) diene complex from Boulder
Scientific Company Batch 459-0140 of 1997.
[0025] The equation for reporting the sample catalyst activity is
as follows: 1 % Activity = Average Sample Activity Average Standard
Activity .times. 100 = Sample Activity
[0026] "Average" means the average of two runs with activities MTS
which are the same within plus or minus 5%.
"Process Description" and "Reaction" for "Standard" CGC
BSC-1459-4-0140 Dated Feb. 26, 1997
[0027] Process Description
[0028] This process involves making reactant slurries 1 and 2 in
separate vessels and then combining these slurries for the final
reaction. Slurry 1 is produced by charging toluene into a vessel
and deoxygenating. Then titanium tetrachloride is added, followed
by adding n-butyllithium. This addition is very exothermic. The
resulting mixture comprising slurry 1 is stirred for 1 hour. This
process is illustrated by equation 1); 3
[0029] Slurry 2 is made up as follows: Toluene and CpSA ligand are
charged to a reaction vessel. After adjusting the pot temperature
to 45-50.degree. C., a solution of isopropylmagnesium chloride in
ethyl ether is fed into the reaction vessel resulting in gas
evolution. Gentle heating is used as needed in order to end up with
a pot temperature of 45-50.degree. C. at the end of the Grignard
feed. The reaction mixture is slowly heated and solvents begin to
distill along with increased gas evolution. The reaction mixture is
heated up to 85-90.degree. C., and this temperature is maintained
for 2 hours. After allowing the reaction mixture to cool to
60-65.degree. C., TiCl.sub.3 is fed into the reaction vessel. The
reaction mixture is then cooled to 20-25.degree. C. This becomes
known as Slurry 2. This process is illustrated by equations 2) and
3); 4
[0030] The agitated Slurry 1 is transferred into the reactor
containing the agitated Slurry 2 as quickly as possible resulting
in about a temperature increase of about 7-15.degree. C. Methylene
chloride is then charred to the reaction vessel, the vessel
containing Slurry 1 is then rinsed out with toluene and charged to
the Slurry 2 reaction vessel, and this mixture is then agitated for
2 hours. A dark reddish-brown color is noted in the reaction vessel
as soon as Slurry 1 is introduced. This reaction is illustrated by
equation 4): 5
[0031] Solvents are removed under reduced pressure (60-80 mm Hg)
using a rotary vane vacuum pump to about 1/2 of the starting
volume. Toluene is added back, Celite is added, and the mixture is
filtered through the large sparkler filter. Solvents are then
distilled to concentrate the product. The remaining crude product
solution is then used directly in the next step.
Process Description" and "Reaction" for Conversion of CGC
Dichiloide to a (Group 4(II) Diene Complex
[0032] Process Description
[0033] The crude product from the previous steps of this process,
equations 1) to 4) which is still contained in the reactor used is
agitated at a pot temperature of 20-25.degree. C. and piperylene
concentrate (1 ,3-pentadiene) is added.
[0034] Butylmagnesium chloride in TKF is fed into the reactor. The
reaction is exothermic. When the Grignard feed is done, the
reaction mixture is agitated for an additional 1/2 hour at a pot
temperature of 35-40.degree. C.
[0035] This mixture is then distillod atmospherically to a pot
temperature of 85.degree. C., cooled to 20-25.degree. C., and then
vacuum distilled at .ltoreq.65.degree. C. One drum of deoxgenated
hydrocarbon solvent and Celite is added at 20-25.degree. C., and
the resulting mixture is filtered through the large 33 inch
sparkler. The filter cake is hydrolyzed. The resulting solution is
then vacuum distilled at .ltoreq.65.degree. C.
[0036] Six drums of deoxygenated Isopar are charged to the reactor,
2 drums at a time, and then vacuum distilled at <65.degree. C.
to remove THF and toluene. When the solvent concentrations are
appropriate, 1 drum of deoxygenated Isopar and Celite are added.
The resulting solution is filtered through a precoated small
sparkler filter into a cylinder. The filter cake may be discarded.
The reaction is illustrated by the following equation 5). 6
SUMMARY OF THE INVENTION
[0037] The invention provides ligands of novel constrained geometry
Group 4(II) diene complexes and complexes derived therefrom which
have an olefin polymerization activity significantly greater than
that demonstrated by known complexes of the same type.
[0038] In particular, the invention provides complexes of the
formula 7
[0039] which have an olefin activity substantially in excess of
100%, e.g., at least about 130%, of the aforesaid "standard
activity".
[0040] Pursuant to one aspect of the invention, a cyclopentadienyl
silyl amine is treated with an alkali metal alkyl and thereafter
with a dialkyl silyl dihalide to produce cyclopentadienyl silyl
amine ligand (CpSA ligand). The ligand is treated with a group 4
metal tetrahalide adduct of a linear ether having at least two
oxygen atoms and an alkali metal alkyl to produce a dihalide ligand
of the ultimately desired group 4(II) complex having the formula:
8
[0041] The dihalide ligand is treated with a diene and an alkali
metal alkyl used in stoichiometric excess. Dienes useful in the
invention are described in U.S. Pat. Nos. 5,470,993 and 6,015,916.
The unreacted alkali metal alkyl in the consequent reaction mixture
is quenched, for example, by chlorotrimethyl silane. The complex so
produced is apparently free or substantially so of impurities which
may result in undesirable gel formation and impair single site
olefin polymerization functionality.
DETAILED DESCRIPTION OF THE INVENTION
[0042] Various group 4 metal tatrachoride-ether adducts are known.
See, generally, U.S. Pat. No. 5,470,993 and published German
application DE 197 30 94 A1. Each of top adducts described in these
references is useful in this invention. The 1,2-dimethoxyethane
(DME) adducts are preferred.
[0043] One method for preparing a DME group 4 metal tetrahalide
adduct is described in U.S. Pat. No. 6,015,916, Col. 4, II. 61-66.
More generally useful adducts are prepared by treating from any
compound of formula X.OYO.OX in which X is a C.sub.1 to C.sub.10
alkyl group, and Y is a C.sub.2 to C.sub.10 alkane.
[0044] Any group 4 tetrahalide-ether adduct may be used. Titanium
tetrachloride DME adducts are preferred. The adduct is preferably
prepared in a hydrocarbon solvent. The mol ratio of the reactants
is preferably about 1:1 with a small excess of the ether
reactant.
[0045] Any alkali metal alkyl having the formula A--R, in which A
may be any alkali metal, preferably lithium, and R is any alkyl
group, preferably a C.sub.1 to C.sub.10 alkyl group, may be used.
N-butyllithium is preferred.
[0046] The synthesis of the dihalo metallocene ligand is conducted
in a non-interfering medium. Suitable media include hydrocarbons,
preferably a C.sub.5 to C.sub.8 alkane, and mixtures of an alkane
and ethyl ether. The synthesis may be performed at any effective
reaction temperature. A preferred temperature range is from
-20.degree. C. to 0.degree. C. The reaction mixture contains the
dihalo ligand in the non-interfering medium. Upon cooling, the
dihalo ligand separates from the reaction mixture as a crystalline
solid which may be removed by filtration under an inert atmosphere,
preferably nitrogen. The isolated dihalo ligand may be
recrystallized to further reduce impurity content.
[0047] The alkali metal alkyl is used in stoichiometric excess to
reduce substantially all of the group 4(IV) dihalo ligand to the
group 4(II) finished catalyst and to reduce any other group 4(IV)
compounds which may be present in the reaction mixture to group
4(II) compounds or other compounds of minimal adverse affect on the
activity or single site functionality of the finished catalyst. The
excess alkali metal alkyl is quenched, for example, with
chlorotrimethyl silane. The product is understood to comprise a
single site catalyst composite essentially free of group 4(IV) or
group 4(III) compounds and other impurities which may adversely
affect single site polymerization activity.
Exemplification of the Invention
[0048] 1. Synthesis of the Cyclopentadienyl Silyl Amine Ligand
[0049] A cyclopentadienyl compound as defined is charged to a
vessel. THF is added, preferably at a temperature from about
-20.degree. C. to -10.degree. C., depending upon the
cyclopentadienyl compound used. Dimethyldichlorosilane is fed in at
a low temperature of about -10.degree. C. to 0.degree. C. The
vessel is agitated and the contents warmed to room temperature and
aluted thereafter. The selected alkylamine, preferably a C.sub.1 to
C.sub.10 alkyl amine, is fed into the vessel at low temperature,
e.g., about -10.degree. C. After agitation and warming to room
temperature, the vessel is heated, and THP and unreacted amine are
removed. A slurry may form. If so, heptane or equivalent
hydrocarbon media may be added. The slurry is filtered. The
filtrate contains cyclopentadienyl silyl amine ligand (CPSA ligand)
of formula: 9
[0050] in which Z is a cyclopentadienyl group and R is an alkyl
group derived from the alkyl amine reactant.
[0051] 2. Preparation of the Dihalo Ligand
[0052] The dihalo ligand may be synthesized in the manner described
in U.S. Pat. No. 6,015,916, Col. 3, I. 60, part (2). In general,
the cyclopentadienyl silyl amine may be treated with an unreduced
group 4 tetrachloride, preferably in the form of a DME or
equivalent adduct in a hydrocarbon solvent. The Ti(IV) of the
dihalo intermediate is converted to Ti(II) in the final complex by
treatment with an alkali metal alkyl as described, preferably
butyllithium, and a diene in a non-interfering, preferably
hydrocarbon, medium at a preferred temperature of -10.degree. C. to
0.degree. C. The alkali metal alkyl is used in stoichiometric
excess to reduce the group 4(IV) ligand to the group 4(II) finished
catalyst and to reduce any other group 4(IV) compounds which may be
present in the reaction mixture. The excess alkali metal alkyl is
quenched, preferably with chlorotrimethylsilane.
Examples Demonstrating Enhanced Polymerization Activity
EXAMPLE 1
[0053] All apparatus used in this example were clean, dry and
nitrogen-purged. Presence of THEF was precluded.
[0054] 21.2 kg of ethyl ether and 6.5 kg of CpSA ligand (assumed
95% purity) were charged into a first reactor. The pot temperature
was reduced to -20.degree. C.
[0055] 21.2 kg of 15% n-butyllithium in hexane was slowly added
with the pot temperature maintained between -20.degree. C. and
-10.degree. C. After the feed was completed, the pot temperature
was raised to 20.degree. C. over 1 hour, and the pot contents were
agitated for 4 hours at 20-25.degree. C. A reaction mixture
containing a CpSA dilithio salt was produced.
[0056] 34.2 kg of deoxygenated heptane and 2.6 kg of
dimethoxyethane were charged into a second reactor. The pot
temperature was adjusted to about 10-15.degree. C.
[0057] 4.8 kg of titanium tetrachloride were charged to the second
reactor at a pot temperature of between 15.degree. C. and
30.degree. C. Upon completion of the feed, the speed of agitation
of the second reactor contents was increased. Agitation continued
for about 3 hours at a pot temperature of 20-25.degree. C.
[0058] The pot temperature of each of the first and second reactors
was adjusted to 15-20.degree. C. Thereafter, the contents of the
first reactor were transferred to the second reactor with the pot
temperature of the second reactor maintained at 20-25.degree. C.
The second reactor contents were then agitated for about 12 hours
at 25-28.degree. C.
[0059] A reactions mixture containing the dichloride ligand having
the formula set forth on page 13 hereof was produced in the second
reactor. After solvent stripping, 47.0 kg of deoxygenated heptane
was added to the second reactor. The second reactor pot temperature
was adjusted to -15.degree. C. Thereafter, 6 kg of piperylene was
charged to the second reactor. 23.3 kg of EM butyllithium in hexane
were fed into the second reactor. During this feed, the pot
temperature was maintained between -15.degree. C. and -10.degree.
C. Upon completion of the food, the pot temperature was adjusted to
20-25.degree. C. over 1 hour. The reaction mixture was agitated for
about three hours at 20-25.degree. C.
[0060] 1.5 kg of trimethylsilicon chloride (TMSCl) was added. The
pot temperature was adjusted to 40-45.degree. C. with agitation for
2 hours. Thereafter, the pot temperature was adjusted to
20-25.degree. C., and the reaction mixture was filtered. The cake
comprising CGC-7 was rinsed with deoxygenated heptane.
[0061] Theory yield--9.1 Kg contained
[0062] Actual yield--7.454 Kg contained.
[0063] Activity (determined as described above)--170%.
EXAMPLE 2
[0064] All apparatus used in this example were clean, dry and
nitrogen-purged. Presence of THF was precluded.
[0065] 8.5 kg of ethyl ether and 2.6 kg of CpSA ligand (95% purity
assumed) were charged into a clean, Isopar-rinsed, nitrogen-purged
first reactor. The pot temperature was -20.degree. C.
[0066] 13.7 kg of deoxygenated Isopar E and 1.0 kg of
dimethoxymethane were charged into a dry, nitrogen-purged second
reactor. The pot temperature was adjusted to 10-15.degree. C.
[0067] 1.9 kg of titanium tetrachloride were fed into the second
reactor with slow agitation of the reactor contents and with the
pot temperature maintained between 15.degree. C. and 30.degree. C.
Upon completion of the feed, the agitation was increased, and the
contents of the second reactor were agitated for about 3 hours at
20-25.degree. C.
[0068] The pot temperature of each of the first and second reactors
was adjusted to 15-20.degree. C. The agitated contents of the first
reactor were transferred to the second reactor with the second
reactor pot temperature maintained At 20-25.degree. C. The contents
of the second reactor were agitated for about 12 hours at
20-28.degree. C. The reaction mixture in the second reactor
contained the dichloride ligand set forth on page 13 hereof.
Solvents were stripped from the reaction mixture.
[0069] The pot temperature of the second reactor was adjusted to
15.degree. C. 2.0 kg of piperylene were charged to the reactor, 8.5
kg of 15% butyllithium in hexane were slowly fed into the second
reactor temperature maintained between -15.degree. C. and
-10.degree. C. After the feed was completed, the pot temperature
was adjusted to 20-25.degree. C. over a 1 hour time period. The
reaction mixture was agitated for 3 hours at 20-25.degree. C.
[0070] 600 g of TMSCl were added, and the reaction mixture was
agitated for 1 hour. The reaction mixture which contained the
desired group 4(II) diene complex was filtered, and the cake was
rinsed with deoxygenated Isopar.
[0071] Theory yield of CGC-7 (contained)--3.65 kg.
[0072] Actual yield of CGC-7 (contained)--2.59 (71% yield)
[0073] Activity (as determined in the manner described
above)--140%.
EXAMPLES 3 AND 4
[0074] Synthesis procedures substantially as described in Examples
1 and 2 yielded Group 4(II) diene complex products having
activities, when determined as described above, of 165% and
130%.
* * * * *