CN1214055A - Stable metallocene catalyst systems - Google Patents
Stable metallocene catalyst systems Download PDFInfo
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- CN1214055A CN1214055A CN97192760A CN97192760A CN1214055A CN 1214055 A CN1214055 A CN 1214055A CN 97192760 A CN97192760 A CN 97192760A CN 97192760 A CN97192760 A CN 97192760A CN 1214055 A CN1214055 A CN 1214055A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
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Abstract
This invention relates to stabilized metallocene catalyst systems and to methods for their production and use. Specifically, these catalyst systems comprise metallocene, alkylalumoxane and optionally support material wherein the ratio of the aluminum of the alkyl alumoxane to the transition metal of the metallocene used to prepare the metallocene is in the range of from about 80:1 to about 200:1. These catalysts retain their activity and may be used directly in polymerization after storage for up to two months or more at ambient temperature.
Description
Invention field:
The present invention relates to the method for stable metallocene catalyst system and production thereof and application.Specifically, these catalyst systems are made up of metallocenes and alkylaluminoxane, and wherein being used for preparing the aluminium of aikyiaiurnirsoxan beta of catalyst system and the ratio of the transition metal in the metallocenes is about 80: 1 to about 200: 1.Storing two months or after longer time, these catalyst systems still keep their activity, and can be directly used in polyreaction.
Background of invention:
One that is associated with the activatory metallocene catalyst system on record problem is, after this system was stored several days or several hours, catalyst system just can not keep stable and keep active, at high temperature especially serious.Therefore, metallocene catalyst system must very fast use after making, to bring into play its maximum productivity.It is quite difficult that catalyzer just comes into operation after preparation at once, particularly difficult when technical scale.Up to the present, the attempt of attempting to address this problem has only obtained limited success.
U.S. Pat 5,308,817 have described a kind of special syndiotaxy metallocenes, and after with the methylaluminoxane activation, this metallocenes can be stablized 3 days, and keeps good activity.But long catalyst system of this time can cause that polymerization reactor produces dirt, and more and more obvious with this trend of the growth of period of storage.
U.S. Pat 5,393,851 have described a kind of concentrated storage liquid of metallocenes/aikyiaiurnirsoxan beta, and this storage liquid can be stored 14 days.Before being used for polyreaction, must adding aikyiaiurnirsoxan beta it is diluted.In addition, this concentrated solution must be stored under the quite low environment of temperature keeping its activity, storage liquid become stable before, 20 to 30% the vigor loss of can having an appointment.
Two patent descriptions discussed above, needs can be stored catalyst system and the component of long period.Specifically, not only need the catalyst system that to store the long period, and need it can store (comprising high temperature) at ambient temperature, and after storage, can be directly used in polyreaction.The application has described beyond thought, an improved reactive metal ocene catalyst system, and this system can at high temperature be stored two months or the longer time.After storage, do not need other activation just this catalyst system directly can be used as effective polymerizing catalyst.
Summary of the invention:
The present invention relates to the polyolefinic method of a kind of catalysis, it comprises: under suitable polymerizing condition, in the presence of metallocene catalyst system active, that form by metallocenes and alkylaluminoxane, and this catalyst system has been stored under two days the situation at least, the method for one or more alkene of catalyzed polymerization.The present invention also relates to stable metallocene catalyst system, this system is made up of metallocenes, alkylaluminoxane and nonessential solid support material, and wherein being used for preparing the aluminium of alkylaluminoxane of catalyst system and the ratio of the transition metal in the metallocenes is about 80: 1 to about 200: 1.In addition, the present invention also relates to prepare the method for metallocene catalyst system, described method may further comprise the steps: (a) metallocene catalyst components is combined with alkylaluminoxane, wherein being used for preparing the aluminium of alkylaluminoxane of catalyst system and the ratio of the transition metal in the metallocenes is about 80: 1 to about 200: 1; (b) store for some time with this in conjunction with product, at least about 2 days.
Detailed description of the preferred embodiments:
Usually, metallocene catalyst system of the present invention is made up of metallocenes and alkylaluminoxane, and wherein being used for preparing the aluminium of alkylaluminoxane of catalyst system and the ratio of the transition metal in the metallocenes is about 80: 1 to about 200: 1.This catalyst system can be stored at least about two days not loss of activity significantly under quite high temperature." storage " of Shi Yonging here is meant when not being used as catalyst system or component the placement of catalyzer.
Preferably, being used for preparing the aluminium of alkylaluminoxane of catalyst system and the ratio of the transition metal in the metallocenes is about 85: 1 to about 150: 1, more preferably about 90: 1 to about 125: 1.Said composition can be stored at least about two days or until about 5 days, about 7 days, about 14 days, about 21 days, about 28 days, about 35 days, about 42 days, about 49 days, about 56 days, about 63 days, about 70 days, about 77 days, about 84 days, even about 91 days or longer.
Preferably, the weight percent of metal is about 0.20 to about 1.0, more preferably about 0.25 to about 0.85 in the final catalyst system, most preferably is about 0.30 to about 0.70.
Temperature during storage may be up to 60 ℃, preferably to 45 ℃, and more preferably envrionment temperature or about 20 ℃ to about 45 ℃.Though catalyst system can be stored under high envrionment temperature, if it is stored under the actual cool condition, this catalyst system may keep higher efficient.Therefore, this catalyst system can be stored in outdoor, or under most of weather conditions, only is that part is sheltered.Any suitable vessel all can be used for storing.For keeping active, container should seal, and storage environment is answered no oxygen and/or water.
After the storage, catalyst system keep being at least its final active about 50%, preferably at least about 60%, more preferably at least about 70%, even more preferably at least about 75%, especially more preferably about 80%, more more preferably at least about 90%, most preferably be at least 95%, just its activity when less than 1 day.
Metallocenes and alkylaluminoxane preferably combine with a kind of carrier, both can be before storage also can combination after storage, preferably combination before storage.For the purpose of patent specification, term " carrier " be defined as any thereon can fixing metal the material of luxuriant and/or activator.Preferably, solid support material is porous prilled material, as talcum, inorganic oxide, butter and resin material, as polyolefine or polymerizable compound.The common commercially available acquisition of such material.
Preferred solid support material is the porous inorganic oxide material, comprises those metal oxides in 2,3,4,5,13 or 14 families of the periodic table of elements.Silica, alumina, silica-alumina and their mixture thereof are most preferred.Other inorganic oxide has magnesium oxide, titanium dioxide, zirconium white etc., and they both can use separately, also can be used in combination with silica, alumina or silica-alumina.
Any metallocenes may be used to practice of the present invention.Except as otherwise noted, " metallocenes " used herein comprises the two or many metalloceness composition of the luxuriant composition of monometallic.Metallocenes is typical bulky ligand transient metal compound, can be expressed from the next usually:
(L)
mM (A)
nWherein L is a kind of bulky part; A is a leavings group, and M is a transition metal, and the size of m and n makes that the valency of whole parts is corresponding with the valency of transition metal.
Ligand L and A bridging mutually, and if two kinds of ligand L and/or A occur, their may bridging.Metallocenic compound can be the compound with complete sandwich type of two or more ligand L, and L can be cyclopentadienyl ligands or cyclopentadienyl derivative part; Perhaps Metallocenic compound can be half a sandwich type compound with a kind of ligand L, and L can be cyclopentadienyl ligands or cyclopentadienyl derivative part.Transition metal atoms can be 4,5 or 6 family's metals and/or be a kind of group of the lanthanides or actinide metals.Zirconium, titanium and hafnium all are usually preferred metals.Other part can be bonded on the transition metal, as leavings group, for example but be not limited to, alkyl, hydrogen or any other monovalent anion part.
The method of making and act on metallocenes has been that this area is in common knowledge.For example, at United States Patent (USP) 4,530,914,4,542,199,4,769,910,4,808,561,4,871,705,4,933,403,4,937,299,5,017,714,5,026,798,5,057,475,5,120,867,5,278,119,5,304,614,5,324,800,5, in 350,723 and 5,391,790 metallocenes was discussed, was here all introduced as reference in full for every piece.
Further, metallocene catalyst components of the present invention can be that a kind of monocyclopentadienyl contains heteroatomic compound.This heteroatoms can be activated by aikyiaiurnirsoxan beta, ionization activator, Lewis acid or their mixture, to form a kind of active polymerisation catalyst system that has.The type specification of these catalyst systems exists, for example international open WO 92/00333, WO94/07928 of PCT, WO 91/04257, WO 94/03506, United States Patent (USP) 5,057,475,5,096,867,5,055,438,5,227,440,5,264,405 and EP-A-0 420 436 in, they all are incorporated herein by reference in full at this.In addition, be used for metalloscene catalyst of the present invention and can comprise non-cyclopentadienyl catalyst component, or assistant ligand, for example borole and carbollide combine with transition metal.
In one embodiment, metallocene catalyst components formula: (C
p)
mM
eR
nR '
pRepresentative, wherein at least one C
pBe non-replacement, or preferably, the cyclopentadienyl rings of replacement; Me is the transition metal of 4,5 or 6 families; R and R ' are selected from hydrogen, alkyl independently of one another or contain the carboxyl (hydrocarboxyl) of 1-20 carbon atom, or their combination; M=1～3, n=0～3, p=0～3, and also m+n+p equals the oxidation state of Me.
In another embodiment, metallocene catalyst components is by formula (C
5R '
m)
pR "
s(C
5R ' is Me Q m)
3-P-xWith formula R " s (C
5R ' m)
2MeQ ' representative, wherein Me is the transition metal of 4,5 or 6 families; At least one C
5R '
mIt is the cyclopentadienyl that replaces; Each R ', can be identical or different, be hydrogen, alkyl, thiazolinyl, aryl, alkaryl or aromatic alkyl group, it contains 1 to 20 carbon atom or two carbon atoms and interosculates and contain the part of the ring of the replacement of 4 to 20 carbon atoms or non-replacement with formation; " be one or more or the group of their bonded carbon atoms, germanium atom, Siliciumatom, phosphorus atom or nitrogen-atoms, this group is with two (C for R
5R '
m) ring or 1 (C
5R '
m) the ring bridging is to Me, as P=0 and x=1 otherwise x always equals 0, each Q can be the identical or different aryl that contains 1 to 20 carbon atom, alkyl, thiazolinyl, alkaryl or aromatic alkyl group, halogen or alkoxide; Q ' is the alkylene group that contains 1-20 carbon atom; S is 0 or 1, when s is 0, m be 5 and p be 0,1 or 2, when s is 1, m be 4 and p be 1.
Preferably, metallocenes is expressed from the next:
Wherein M is the metal that is selected from the periodic table of elements 4,5 or 6 families, is preferably zirconium, hafnium and titanium, most preferably is zirconium.
R
1And R
2Identical or different, be hydrogen atom, C
1-C
10The preferred C of alkyl
1-C
3Alkyl, C
1-C
10The preferred C of alkoxyl group
1-C
3Alkoxyl group, C
6-C
10The preferred C of aryl
6-C
8Aryl, C
6-C
10The preferred C of aryloxy
6-8Aryloxy, C
2-C
10The preferred C of alkene
2-C
4Alkenyl, C
7-C
40The preferred C of aralkyl
7-C
12Aralkyl, C
7-C
40Alkaryl, preferred C
7-C
12Alkaryl, C
8-C
40The preferred C of aromatic yl alkenyl
8-C
12The preferred chlorine atom of aromatic yl alkenyl or halogen atom;
R
3And R
4Be hydrogen atom;
R
5And R
6Be identical or different, but preferred identical, be the preferred fluorine atom of halogen atom, fluorine atom or bromine atoms, can be by halogenated C
1-C
10The preferred C of alkyl
1-C
4Alkyl, can be by halogenated C
6-C
106-C under the preferred C of aryl
8Aryl, C
2-C
10The preferred C of alkenyl
2-C
4Alkenyl, C
7-C
40The preferred C of aralkyl
7-C
10Aralkyl, C
7-C
40The preferred C of alkaryl
7-C
12Alkaryl, C
8-C
40The preferred C of aromatic yl alkenyl
8-C
12Aromatic yl alkenyl ,-NR
2 15,-SR
15,-OR
15,-OSiR
3 15Or-PR
2 15Group, wherein R
15Be the preferred chlorine atom of halogen atom, C
1-C
10The preferred C of alkyl
1-C
3Alkyl or C
6-C
10The preferred C of aryl
6-C
9Aryl;
R
7For
-B (R
11)-,-Al (R
11)-,-Ge-,-Sn-,-O-,-S-,-SO-,-SO
2-,-N (R
11)-,-CO-,-P (R
11)-, or-P (O) (R
11)-; R wherein
11, R
12And R
13Identical or different, be hydrogen atom, halogen atom, C
1-C
20The preferred C of alkyl
1-C
10Alkyl, C
1-C
20The preferred C of fluoro-alkyl
1-C
10Fluoro-alkyl, C
6-C
30The preferred C of aryl
6-C
20Aryl, C
6-C
30The preferred C of fluorinated aryl
6-C
20Fluorinated aryl, C
1-C
20The preferred C of alkoxyl group
1-C
10Alkoxyl group, C
2-C
20The preferred C of alkenyl
2-C
10Alkenyl, C
7-C
40The preferred C of aralkyl
7-C
20Aralkyl, C
8-C
40The preferred C of aromatic yl alkenyl
8-C
22Aromatic yl alkenyl, C
7-C
40The preferred C of alkylaryl
7-C
20Alkylaryl, perhaps R
11And R
12Or R
11And R
13Can form the ring-type system with the atom that they are connected together;
M
2Be silicon, germanium or tin, preferred silicon and germanium, most preferably silicon.
R
8And R
9Identical or different, and have and R
11Identical implication;
M and n are identical or different, and are 0,1 or 2, are preferably 0 or 1, and m+n is 0,1 or 2, is preferably 0 or 1; With
R
10Group is identical or different, and has and R
11, R
12And R
13Identical implication, and two adjacent R wherein
10Base can connect together and form the ring-type system, is preferably the ring-type system of 4-6 carbon atom.
Alkyl refers to the substituting group of straight or branched.Halogen (halo) is fluorine, chlorine, bromine or iodine atom, preferred fluorine or chlorine.
Especially preferred metallocenes is the compound of array structure under the tool:
M wherein
1Be Zr or Hf, R
1And R
2Be methyl or chlorine, and R
5, R
6, R
8, R
9, R
10, R
11And R
12Above-mentioned implication is arranged.
The luxuriant racemoid of chiral metal as the highly isotactic polypropylene copolymer of preparation.Can also use simple R or S form.Can prepare a kind of nonessential active polymkeric substance with these simple stereomeric forms.Preferably the metallocenes of meso-form is removed to guarantee that center (being atoms metal) provides stereoregulated polymerization.Can utilize the technology of putting down in writing in the known document to realize the separation of steric isomer.Also can use racemize/meso mixture for specialty products.
In general, prepare metallocenes by the rapid method of a kind of multistep, this method comprises that the proton/metal of taking off repeatedly of aromatics ligand replaces and introduces bridge atom and central atom by its halogen derivative.Following reaction scheme has shown this general approach:
H
2R
c+ butyl Li--------＞HR
cLi
X-(CR
8R
9)
m-R
7-(CR
8R
9)
n-X
------------------＞H
2R
d+ butyl Li-------＞HR
dLiHR
c-(CR
8R
9)
m-R
7-(CR
8R
9)
n-R
dH 2 butyl Li
-------＞LiR
c-(CR
8R
9)
m-R
7-(CR
8R
9)
n-RdLi???M
1Cl
4
-------＞
Other method of preparation metallocenes fully is described in
The organometallic chemistry magazine, the
288 volumes(1958), 63-67 page or leaf, and EP-A-320762, for preparing above-mentioned metallocenes, these two pieces of documents all are incorporated herein by reference.
Metallocenes illustrative but example indefiniteness comprise: two (2-methyl-4-phenyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4, the 5-benzo indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4, the 6-di-isopropyl indenyl) ZrCl of dimethyl silyl base
2, two (2-ethyl-4-phenyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-ethyl-4-naphthyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4-phenyl-1-indenyl) ZnCl of phenyl (methyl) silicomethane two bases
2, two (2-methyl-4-(1-the naphthyl)-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4-(2-the naphthyl)-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4, the 5-di-isopropyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2,4, the 6-trimethylammonium-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4, the 6-di-isopropyl-1-indenyl) ZrCl of phenyl (methyl) silicomethane two bases
2, 1, two (2-methyl-4, the 6-di-isopropyl-1-indenyl) ZrCl of 2-second two bases
2, 1, two (2-methyl-4, the 6-di-isopropyl-1-indenyl) ZrCl of 2-fourth two bases
2, two (2-methyl-4-ethyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4-sec.-propyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (the 2-methyl-4-tertiary butyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4-sec.-propyl-1-indenyl) ZrCl of phenyl (methyl) silicomethane two bases
2, two (2-ethyl-4-methyl isophthalic acid-indenyl) ZrCl of dimethyl silyl base
2, two (2, the 4-dimethyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4-ethyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-α-acenaphthenyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-4, the 5-phendioxin-indenyl) ZrCl of phenyl (methyl) silicomethane two bases
2, two (2-methyl-4,5-(methyl the benzo)-1-indenyl) ZrCl of phenyl (methyl) silicomethane two bases
2, two (2-methyl-4,5-(tetramethyl-the benzo)-1-indenyl) ZrCl of phenyl (methyl) silicomethane two bases
2, two (2-methyl-α-acenaphthenyl-1-indenyl) ZrCl of phenyl (methyl) silicomethane two bases
2, 1, two (2-methyl-4, the 5-phendioxin-indenyl) ZrCl of 2-second two bases
2, 1, two (2-methyl-4, the 5-phendioxin-indenyl) ZrCl of 2-fourth two bases
2, two (2-methyl-4, the 5-phendioxin-indenyl) ZrCl of dimethyl silyl base
2, 1, two (2,4, the 7-trimethylammonium-1-indenyl) ZrCl of 2-second two bases
2, two (2-methyl isophthalic acid-indenyl) ZrCl of dimethyl silyl base
21, two (2-methyl isophthalic acid-indenyl) ZrCl of 2-second two bases
2, two (2-methyl isophthalic acid-indenyl) ZrCl of phenyl (methyl) silicomethane two bases
2, two (2-methyl isophthalic acid-indenyl) ZrCl of diphenylmethyl silane two bases
2, 1, two (2-methyl isophthalic acid-indenyl) ZrCl of 2-fourth two bases
2, two (2-ethyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-5-isobutyl--1-indenyl) ZrCl of dimethyl silyl base
2, two (2-methyl-5-isobutyl--1-indenyl) ZrCl of phenyl (methyl) silicomethane two bases
2, two (the 2-methyl-5-tertiary butyl-1-indenyl) ZrCl of dimethyl silyl base
2, two (2,5, the 6-trimethylammonium-1-indenyl) ZrCl of dimethyl silyl base
2Deng.
These preferred metalloscene catalyst compositions U.S.5145819,5243001,5239022,5329033,5296434,5276208 and 5374752 and EP549900 and 576970 in have a detailed description, all these documents all are incorporated herein by reference.
Alkylaluminoxane can be used as the activator of metallocenes, it contains 5-40 the following formula repeating unit of having an appointment usually: be used for linear kind
Be used for the ring-type kind
Wherein R is C
1-C
8Alkyl comprises the blended alkyl.Particularly preferably being wherein, R is the compound of methyl.Aluminoxanes solution, especially preferable methyl aluminoxanes solution can various concentration be buied from market.The various methods that prepare aikyiaiurnirsoxan beta are arranged, the example of the indefiniteness of such method U.S.4665208,4952540,5091352,5206199,5204419,4874734,4924018,4908463,4968827,5308815,5329032,5248801,5235081,5157137,5103031 and EP-A-0561476, EP-B1-0279586, EP-A-0594218 and WO 94/10180 in description is arranged, these documents all are incorporated herein by reference.
Some methylaluminoxane (MAO) solution becomes muddy and agglutination easily after after a while.It is favourable making this class solution clarification before use.Can make in many ways for the MAO solution that forms gel-free or in order from solution, to remove gel.The band gel solution usually filtered simply or decant from limpid MAO, to remove gel.U.S.5157137 discloses a kind of method that forms the alkylalumoxane solution of clarifying gel-free by the solution of handling alkylaluminoxane with the anhydrous salt and/or the hydride of basic metal or alkaline-earth metal.
Metallocenes, alkylaluminoxane and solid support material can be in any way or the order combination.The case description of suitable bearing technology is in U.S. Pat 4,808, in 561 and 4,701,432 (every piece all is incorporated herein by reference in full).Metallocenes and the combination of alkylaluminoxane elder generation combine its reaction product then with loading material but preferably.The suitable case description of this technology is in U.S. Pat 5,240,894 and WO 94/28034, WO 96/00243 and WO 96/00245 (every piece all is incorporated herein by reference in full) in.
Preferably, use as silicon-dioxide and be less than 4.0 times carrier total pore volume, be more preferably less than 3.0 times carrier total pore volume, especially be more preferably less than 2.5 times carrier total pore volume as the cumulative volume of porous support and carrier-bound metallocenes and activator.
The method of measuring total pore volume of porous support is well known in the art.A kind of details in these methods exist
Experimental technique in the catalyticing research, the first roll (Academic Press, 1968)In description (particularly referring to the 67-96 page or leaf) is arranged.This preferable methods comprises the traditional BET equipment that is used for the nitrogen absorption.Another kind of method well known in the art is described in Innes's
The overall porosity and the pellet density of liquid titration measuring fluid catalyst, the 28th volume, No.3 analyzes Chemistry is in the 332-334 page or leaf (in March, 1956).
When with the volume of porous carrier materials bonded solution during less than the whole pore volume of carrier, solid support material looks like dried fully and can unrestricted flow, therefore mixes easily and transports.When liquor capacity during, mix and transport along with the increase carrier of liquor capacity becomes more and more difficult, because it has the denseness of wet mud greater than 1 times the whole pore volume of carrier.When the volume of solution is bigger, finally form slurry, along with the sedimentation of silica can be clearly seen that solution separates with carrier.Under slurry state, easier mixing of carrier and processing.When selecting liquor capacity, need consider these factors.
No matter use many a spot of solution,, make solution uniformly distributing in carrier granule so preferably with carrier and solution combination.Therefore preferably solution is added in the carrier lentamente, when carrier mixes, can use the mode of spray or dropping to add solution.
After catalyst system is finished carrying, be dried preferably that at least arbitrarily mobile is Powdered, store then.Heating and/or vacuum may be used to dry catalyst.Typically, to about 100 ℃ temperature range, be dried about 4 to 36 hours at about 25 ℃.It may be useful using the hot noble gas of mobile to come dry catalyst rather than vacuum as nitrogen.
After the drying, be preferably about 15 to about 170, more preferably about 50 to about 150, especially more preferably about 80 to about 125 with the final weight ratio of aluminium in the measured alkylaluminoxane of ultimate analysis and the metal in the metallocenes.
Catalyst system of the present invention can be directly used in polymerization or use method well known in the art before storage or store the back by prepolymerization after the storage.About prepolymerized details, with reference to U.S. Pat 4,923,833 and US4,921,825, EP 0279863 and EP 0 354 893, every piece all is incorporated herein by reference in full.Catalyst system of the present invention also can or be stored back and one or more additive combinations, such additive such as scavenging agent before storage.The example of suitable scavenger compounds comprises: triethyl aluminum (TEAL), trimethyl aluminium (TMAL), triisobutyl aluminium (TIBAL), tri-n-hexyl aluminum (TNHAL) or the like.
Catalyst body tie up to can be used for after the storage any monomer of catalysis and, not necessarily, monomer polymerization altogether, catalyzed reaction can be carried out with any method, comprises that gas phase, slurry or solution are mutually or methods such as autoclave.(" polymerization " used herein unless distinguish, comprises copolymerization, and " monomer " comprises common monomer).Preferably, use gas phase or slurry process, more preferably use body propylene liquid polymerization process.
In this embodiment preferred,, the present invention is directed to polymerization and copolymerization, the especially propylene of body propylene liquid or ethene in slurry or vapour phase polymerization or polyreaction, especially during slurry polymerization.Another embodiment relates to propylene or ethene, especially propylene, with one or more 4-20 carbon atom arranged, the polymerization of the 'alpha '-olefin monomers of preferred 4-12 carbon atom, described monomer are for example ethene, butene-1, amylene-1,4-methylpentene-1, alkene-1, octene-1, decylene-1 and as these alpha-olefin copolymer monomers of the alkene of vinylbenzene, cyclopentenes or norbornylene.That other suitable monomers can comprise is vinyl-based, diolefinic such as diolefine such as 1,3-butadiene, 1,4-hexadiene, norbornadiene or vinyl norbornene, acetylene, ethylidene norbornene and aldehydes monomer.
Typically, in gas phase polymerization process, use continuous circulation process, in certain part of reactor cycles, circulating current just recirculated fluid or fluidization medium is aggregated the reaction heating in reactor.Recirculated fluid contains one or more common monomers usually, and these monomers circulate continuously by fluidized-bed under reaction conditions, in the presence of catalyzer.Heat is removed by the cooling system outside the reactor in working cycle.Recirculated fluid derives from fluidized-bed, and then reactor is advanced in circulation.Simultaneously, polymer product is derived from reactor, fresh monomer is added to replace having taken place the polymeric monomer.(reference, for example, United States Patent (USP) 4,543,399,4,588,790,5,028,670,5,352,749,5,405,922 and 5,436,304, all full text are introduced as reference).
Slurry phase polymerisation process carries out under about 1 to 500 normal atmosphere or higher pressure usually, and temperature of reaction is generally-60 ℃ to about 280 ℃ approximately.In slurry polymerization, in liquid polymerizaton medium, can generate suspended solid, granulated polymer, in above-mentioned polymerisation medium, add ethene, be total to monomer and common hydrogen and catalyzer.The liquid that uses in polymerisation medium can be, for example, and a kind of alkane or naphthenic hydrocarbon.The medium that uses should be liquid under polymerizing condition and be relative inertness.The example of nonrestrictive liquid medium comprises hexane and Trimethylmethane.
Preferably, in the productivity of storing the rear catalyst system at least about 2000g polymkeric substance/g catalyzer, more preferably at least about 2500g polymkeric substance/g catalyzer, most preferably at least about 3000g polymkeric substance/g catalyzer.
Embodiment:
In order to provide the present invention better to be understood and comprises its representative advantages, we provide the following example: Preparation of Catalyst: embodiment 1:
In nitrogen glove box, toluene solution (Albemarle Corporation company with the DMAD-25010 of dimethyl silyl base-two (2-methyl-4-phenyl-indenyl) zirconium dichlorides of 0.5g and 18.50g 30wt%, Baton Rouge, LA) combination under agitation condition.The mol ratio of Al/Zr is 110 in solution.Under agitation condition, the scarlet precursor that produces is slowly joined MS 948 silicas (the Davision Chemical Division ofW.R.Grace of 10.0g, Baltimore, MD) in, silica needs to dewater in flowing nitrogen stream through 600 ℃ of high temperature in advance.Slurry is dry under the vacuum of the 28-29 inch of mercury, up to obtaining the solid that 15.56g is free flowable, fine powder is broken.The amount of volatile matter reduces to 1.1wt% in the test shows solid.Ultimate analysis shows and contains 15.41% Al and 0.55% Zr in the product.Embodiment 2:
In nitrogen glove box, toluene solution (Albemarle Corporation company with the DMAD-25010 of dimethyl silyl base-two (2-methyl-4-phenyl-indenyl) zirconium dichlorides of 0.379g and 14.10g 30wt%, Baton Rouge, LA) combination under agitation condition.The mol ratio of Al/Zr is 110 in solution.Under agitation condition, the scarlet precursor that produces is slowly joined MS 948 silicas (the Davision Chemical Division ofW.R.Grace of 10.0g, Baltimore, MD) in, silica needs to dewater in flowing nitrogen stream through 600 ℃ of high temperature in advance.Slurry is dry under the vacuum of the 28-29 inch of mercury, up to obtaining the solid that 15.56g is free flowable, fine powder is broken.Ultimate analysis shows and contains 16.55% Al and 0.29% Zr in the product.The comparative example 3:
In nitrogen glove box, toluene solution (Albemarle Corporation company with the DMAD-25010 of dimethyl silyl base-two (2-methyl-4-phenyl-indenyl) zirconium dichlorides of 0.25g and 18.53g 30wt%, Baton Rouge, LA) combination under agitation condition.The mol ratio of Al/Zr is 217 in solution.Under agitation condition, the scarlet precursor that produces is slowly joined MS 948 silicas (the Davision Chemical Division ofW.R.Grace of 10.0g, Baltimore, MD) in, silica needs to dewater in flowing nitrogen stream through 600 ℃ of high temperature in advance.Slurry is dry under the vacuum of the 28-29 inch of mercury, up to obtaining the solid that 15.61g is free flowable, fine powder is broken.The amount of volatile matter reduces to 0.7wt% in the test shows solid.Ultimate analysis shows and contains 15.77% Al and 0.19% Zr in the product.Embodiment 4:
In nitrogen glove box, toluene solution (AlbemarleCorporation company with the MAO of dimethyl silyl base-two (2-methyl-indenyl) zirconium dichlorides of 0.26g and 13.25g 30wt%, Baton Rouge, LA) under agitation condition in conjunction with and add 5.60g toluene.The mol ratio of Al/Zr is 126 in solution.Under agitation condition, the scarlet precursor that produces is slowly joined MS 948 silicas (the Davision Chemical Division ofW.R.Grace of 10.0g, Baltimore, MD) in, silica needs to dewater in flowing nitrogen stream through 600 ℃ of high temperature in advance.Slurry is dry under the vacuum of the 28-29 inch of mercury, up to obtaining the solid that 14.94g is free flowable, fine powder is broken.Ultimate analysis shows and contains 16.49% Al and 0.45% Zr in the product.The comparative example 5
In nitrogen glove box, dimethyl silyl base-two (2-methyl-indenyl) zirconium dichloride of 850g combined with 15 gallons of toluene and with toluene solution (the Albemarle Corporation company of the methylsiloxane of 30wt%, Baton Rouge, LA) adding is 210 precursor with the mol ratio that forms Al/Zr.(DavisionChemical Division of W.R.Grace, Baltimore MD) join in 200 gallons the reactor, and silica needs dewater in flowing nitrogen stream through 600 ℃ of high temperature in advance with 150 pounds MS 948 silicas in addition.Under agitation precursor is added in the silica.When reactor jacket is heated to 160-165 °F, reactor is applied 28-29 inch mercury vacuum.7.5 collected the catalyzer of free flowing powder form after hour.The amount of volatile matter reduces to 3.35wt% in the test shows solid.Ultimate analysis shows and contains 9.28% Al and 0.17% Zr in the product.Catalyst stability is estimated:
In baking oven, charge into nitrogen and constant temperature at 100 °F (34 ℃), be filled with the stainless steel column of catalyzer to study its stability with its heating.In being full of the glove box of nitrogen, with catalyst loading in stainless steel column.Make the nitrogen pressure of pillar band 15psi before sealing, catalyzer is polluted when preventing from air to handle stainless steel column.Through the time that presets, stainless steel column is taken out from baking oven, and forward in the glove box, catalyzer is taken a sample.Stainless steel column is put back to baking oven continue heating.According to following method, the catalyst sample after aging is carried out the detection of polymerization activity.Polymerization catalyst is estimated:
Will be through N
22 liters of autoclave reactors that purge and contained triethyl aluminum (the 1M hexane solution of 0.25ml) and the propylene of 1000ml are heated to 70 ℃.75mg as above prepared with the aged catalyst sample join in the 2ml hexane and slurryization, and feed the 250ml propylene and begin to react.1 hour postcooling reactor ventilates and uses N
2Purge and open reactor after 20 minutes.Granular polypropylene is transferred in the porcelain dish, spent the night at the stink cupboard inner drying.Second day, with polymkeric substance under vacuum and 75 ℃ of conditions dry 1 hour again.With final dry polymer weighing.Polymerization result: table 1 has been summed up through 100 (34 ℃) the aging active stability of rear catalyst.
Table 1
| Catalyzer embodiment | ?Al/Zr (a) | Production efficiency after the time shown in the heat aging (b) | |||||
| 0 | 40 | 85 | 157 | 250 | 325 | ||
| ??1 | ?110 | 3144 | nd (c) | nd | 3115 | 3056 | 3105 |
| Contrast 3 | ?217 | 2680 | 1895 | 1811 | 1672 | 1736 | 1540 |
(a) mol ratio of precursor
(b) catalyzer of gram polypropylene/gram after the time shown in 100 (34 ℃) heat agings
(c) do not survey
Data show, catalyzer with embodiment 1 of lower aluminium/zirconium molar ratio is stable behind 100 (34 ℃) heat agings, and the catalyzer that is three times among the comparative example 3 of above-mentioned molar ratio has been lost 30% catalyst activity after the burin-in process through 40 hours, and after about 2 weeks, lost about 45% catalyst activity.
The catalyzer of embodiment 1 is continued to carry out senile experiment, result such as table 2 under 100 (34 ℃) conditions.
Table 2
| My god | Production efficiency (a) |
| ????21.4 | ????3017 |
| ????28.4 | ????2813 |
| ????34.4 | ????2704 |
| ????42.3 | ????2723 |
| ????56.3 | ????2696 |
| ????65.2 | ????2873 |
| ????90.2 | ????2109 |
(a) production efficiency (gram polypropylene/gram catalyzer)
The catalyzer of embodiment 2 is listed in table 3 through the experimental result of 100 heat agings.
Table 3
(a) production efficiency (gram polypropylene/gram catalyzer)
| My god | Production efficiency (a) |
| ????0 | ????3216 |
| ????5.8 | ????2819 |
| ????18.7 | ????2443 |
| ????32.6 | ????2480 |
| ????43.5 | ????2528 |
| ????53.4 | ????2647 |
| ????68.4 | ????2419 |
Data show that except very little loss of activity, catalyzer is experiencing the activity that still can remain valid behind two wheat harvesting periods under 100 (34 ℃) conditions.
With the different metallocenes of another kind, after the heat aging that experiences 100 (34 ℃) was handled, the experimental result that compares was listed in table 4.
Table 4
| My god | Embodiment 3 | The comparative example 4 |
| ????3 | ???? (a)????- | ????1788 (b) |
| ????5 | ????3984 | ????- |
| ????7.7 | ????3903 | ????- |
| ????10 | ????- | ????1560 |
| ????15.7 | ????3863 | ????- |
| ????21 | ????- | ????1353 |
| ????22.6 | ????3589 | ????- |
| ????28.1 | ????- | ????1197 |
| ????33.8 | ????3180 | ????- |
| ????35 | ????- | ????1140 |
| ????42 | ????- | ????1141 |
| ????43.6 | ????3647 | ????- |
| ????53.5 | ????3677 | ????- |
| ????60 | ????- | ????869 |
| ????68.4 | ????3373 | ????- |
(a) do not survey
(b) production efficiency (gram polypropylene/gram catalyzer)
The Al/Zr mol ratio is that the catalyzer comparison of 126 embodiment 4 is more stable to loss of activity than the catalyzer of embodiment 5.The latter's Al/Zr ratio is 210, and through the about activity of loss about 50% behind 2 months heat agings, and the catalyzer with ratio of the present invention is keeping about 85% activity through after the identical time.
Although the present invention is described and illustrates that those skilled in the art should know that invention itself comprises many unaccounted different variations here with reference to particular.Therefore, in order to determine the real protection domain of the present invention, should only be as the criterion with appended claims.
Although according to patent practice, appended claims are that single dependency is arranged, and each feature of arbitrary attached claim can combine with each feature of other attached claim or principal claim.
Claims (18)
1. the method for a polymerization alkene, this method comprises: under suitable polymerizing condition, one or more alkenes are contacted with the reactive metal cyclopentadienyl catalyst, and this catalyzer is made up of metallocenes and alkylaluminoxane, and this active catalyst system was stored two days at least.
2. the process of claim 1 wherein period of storage at least 14 days.
3. the process of claim 1 wherein period of storage at least 35 days.
4. the process of claim 1 wherein period of storage at least 56 days.
5. aforesaid right requires each method, and the ratio that wherein is used for preparing transition metal in the aluminium of alkylaluminoxane of catalyst system and the metallocenes is about 85: 1 to 150: 1.
6. aforesaid right requires each method, and wherein catalyst system further comprises solid support material.
7. aforesaid right requires each method, and wherein to tie up to temperature be to store in 20 ℃ to 45 ℃ the scope to catalyst body.
8. the method for claim 4 is before wherein the production efficiency of catalyst system is at least and stores 75% of its initial production efficient.
9. method for preparing metallocene catalyst system, this method may further comprise the steps:
(a) metallocene catalyst components is combined with alkylaluminoxane, wherein the ratio of aluminium in the alkylaluminoxane and the transition metal in the metallocenes is 80: 1 to 200: 1;
(b) store above-mentioned binding substances more than at least two days.
10. the method for claim 9, wherein period of storage is at least 7 days.
11. the method for claim 9, wherein period of storage is at least 21 days.
12. the method for claim 9, wherein period of storage is at least 49 days.
13. the method for claim 9, wherein period of storage is at least 56 days.
14. the method for claim 9-13, wherein in the alkylaluminoxane in aluminium and the metallocenes ratio of transition metal be 90: 1 to 125: 1.
15. the method for claim 9-14 further comprises metallocenes and alkylaluminoxane are combined with solid support material.
16. the method for claim 9-15, wherein solid support material is a porous inorganic oxide, and metallocenes combines with alkylaluminoxane elder generation, and its reaction product combines with porous support again.
17. the method for claim 9-16, wherein binding substances is stored in temperature is 20 ℃-45 ℃ scope.
18. metallocene catalyst system according to the method preparation of claim 9.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1276096P | 1996-03-04 | 1996-03-04 | |
| US60/012,760 | 1996-03-04 |
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| Publication Number | Publication Date |
|---|---|
| CN1214055A true CN1214055A (en) | 1999-04-14 |
Family
ID=21756552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97192760A Pending CN1214055A (en) | 1996-03-04 | 1997-03-04 | Stable metallocene catalyst systems |
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|---|---|
| EP (1) | EP0885248A1 (en) |
| JP (1) | JP2000506212A (en) |
| KR (1) | KR19990087458A (en) |
| CN (1) | CN1214055A (en) |
| AU (1) | AU1988097A (en) |
| CA (1) | CA2243519A1 (en) |
| EA (1) | EA199800808A1 (en) |
| WO (1) | WO1997032906A1 (en) |
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| TWI230712B (en) | 1998-09-15 | 2005-04-11 | Novartis Ag | Polymers |
| KR100328866B1 (en) * | 1999-07-02 | 2002-03-20 | 유현식 | Polymerization process of syndiotactic polystyrene derivatives using microfluidization |
| CN101541838B (en) * | 2006-11-14 | 2013-10-30 | 尤尼威蒂恩技术有限公司 | Catalyst systems and polymerization processes |
| EP2573091A1 (en) | 2011-09-23 | 2013-03-27 | Lummus Novolen Technology Gmbh | Process for recycling of free ligand from their corresponding metallocene complexes |
| WO2020056119A1 (en) | 2018-09-14 | 2020-03-19 | Fina Technology, Inc. | Polyethylene and controlled rheology polypropylene polymer blends and methods of use |
| CA3121960A1 (en) | 2019-02-20 | 2020-08-27 | Fina Technology, Inc. | Polymer compositions with low warpage |
| CN117222697A (en) | 2021-04-26 | 2023-12-12 | 弗纳技术股份有限公司 | Single site catalyzed polymer sheet |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4665047A (en) * | 1986-08-15 | 1987-05-12 | Shell Oil Company | Stabilization of metallocene/aluminoxane catalysts |
| DE4119343A1 (en) * | 1991-06-12 | 1992-12-17 | Basf Ag | INSULATED, SUPPORTED CATALYST SYSTEM FOR THE POLYMERIZATION OF C (DOWN ARROW) 2 (DOWN ARROW) - TO C (DOWN ARROW) 1 (DOWN ARROW) (DOWN ARROW) 0 (DOWN ARROW) -ALK-1-END |
| US5308817A (en) * | 1992-05-18 | 1994-05-03 | Fina Technology, Inc. | Metallocene catalyst component with good catalyst efficiency after aging |
| US5240894A (en) * | 1992-05-18 | 1993-08-31 | Exxon Chemical Patents Inc. | Method for making and using a supported metallocene catalyst system |
| US5393851A (en) * | 1992-05-26 | 1995-02-28 | Fina Technology, Inc. | Process for using metallocene catalyst in a continuous reactor system |
| JPH08208733A (en) * | 1995-01-31 | 1996-08-13 | Mitsubishi Chem Corp | Olefin polymerization catalyst |
| JP3472941B2 (en) * | 1995-03-08 | 2003-12-02 | 三井化学株式会社 | Storage method of olefin polymerization catalyst, olefin polymerization catalyst solution, olefin polymerization catalyst, and olefin polymerization method |
| JP3483013B2 (en) * | 1995-04-28 | 2004-01-06 | 出光石油化学株式会社 | Method for preserving homogeneous catalyst for polymerization |
| CA2225493A1 (en) * | 1995-08-10 | 1997-02-20 | Exxon Chemical Patents, Inc. | Metallocene stabilized alumoxane |
-
1997
- 1997-03-04 EP EP97908032A patent/EP0885248A1/en not_active Ceased
- 1997-03-04 AU AU19880/97A patent/AU1988097A/en not_active Abandoned
- 1997-03-04 WO PCT/US1997/003486 patent/WO1997032906A1/en not_active Application Discontinuation
- 1997-03-04 CA CA002243519A patent/CA2243519A1/en not_active Abandoned
- 1997-03-04 EA EA199800808A patent/EA199800808A1/en unknown
- 1997-03-04 CN CN97192760A patent/CN1214055A/en active Pending
- 1997-03-04 JP JP9531922A patent/JP2000506212A/en active Pending
- 1997-03-04 KR KR1019980706882A patent/KR19990087458A/en not_active Application Discontinuation
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| AU1988097A (en) | 1997-09-22 |
| EA199800808A1 (en) | 1999-04-29 |
| CA2243519A1 (en) | 1997-09-12 |
| WO1997032906A1 (en) | 1997-09-12 |
| KR19990087458A (en) | 1999-12-27 |
| JP2000506212A (en) | 2000-05-23 |
| EP0885248A1 (en) | 1998-12-23 |
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