CN1231678A - Improved method for preparing supported metallocene catalyst system - Google Patents
Improved method for preparing supported metallocene catalyst system Download PDFInfo
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- CN1231678A CN1231678A CN97198171A CN97198171A CN1231678A CN 1231678 A CN1231678 A CN 1231678A CN 97198171 A CN97198171 A CN 97198171A CN 97198171 A CN97198171 A CN 97198171A CN 1231678 A CN1231678 A CN 1231678A
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- 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
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- C08F4/00—Polymerisation catalysts
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- 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
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- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/63916—Component covered by group C08F4/62 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
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- C08F4/00—Polymerisation catalysts
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- 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
- C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
- C08F4/6392—Component covered by group C08F4/62 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/63922—Component covered by group C08F4/62 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
- C08F4/63927—Component covered by group C08F4/62 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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Abstract
This invention relates generally to supported metallocene catalyst systems and to methods for their production and use. Specifically, this invention relates to a method for preparing supported metallocene catalyst systems using an aliphatic solvent. The catalyst systems prepared by these methods exhibit increased activity.
Description
Field of the present invention
The present invention relates generally to metallocene catalyst system on the carrier and their preparation method and purposes.Specifically, the present invention relates to use aliphatic solvents to prepare the method for the metallocene catalyst system on the carrier.
Background
Reported the method for the metallocene catalyst system on many preparation carriers so far.For example the US patent 5,240, and 894 have described wherein, and metallocenes contacts and the method that is deposited on then on the solid support material in advance with activator.This catalyst system drying is then removed residual solvent and is at random carried out prepolymerization.WO94/28034 has described wherein the metallocenes similar approach of the two indenyl compounds of bridge joint specifically.US patent 5,373,072 has been described the method for using the silica gel that do not dewater.US patent 5,468,702 has been described the purposes aspect the metallocene catalyst system of aged activator on the preparation carrier.US patent 5,516,737 has been described the method that supports activator and metallocenes separately.
In all these patents, aromatic hydrocarbon typically is toluene, not only is used as the solvent of aikyiaiurnirsoxan beta (alumoxane) activator but also is used as metallocenes and the solvent of aikyiaiurnirsoxan beta reaction.Typically, metallocenes and aikyiaiurnirsoxan beta are to be deposited on the solid support material in toluene solution.Toluene is the solvent of selecting, because it dissolves aikyiaiurnirsoxan beta and/or activatory metallocenes easily.In case catalyst component is deposited on the carrier, catalyst system carried out drying usually before using, usually significantly reduce the activity of catalyst system although be known that drying conditions.
The inventor has been found that the activity of the metallocene catalyst system on the carrier will significantly improve when aliphatic solvents replaces typical solvent such as toluene or mixes with the latter.
General introduction
The present invention relates to form the method for the metallocene catalyst system on the carrier, this method comprises: (a) allow the reaction of metallocenes and alumoxane activator form catalyst solution; (b) allow catalyst solution in the presence of aliphatic solvents, mix with solid support material.
In another embodiment, the present invention relates to form the method for the metallocene catalyst system on the carrier, comprise that (a) allows metallocenes and alumoxane activator reaction form catalyst solution; (b) allow aliphatic hydrocarbon solvent mix with solid support material; (c) allow catalyst solution mix with mixture.
In another embodiment, the present invention relates to form the method for the metallocene catalyst system on the carrier, this method comprises: (a) allow metallocenes and first part's aikyiaiurnirsoxan beta reaction form first catalyst solution; (b) allow aliphatic solvents and solid support material mix and form mixture; (c) allow first catalyst solution mix with mixture; (d) adds the second section aikyiaiurnirsoxan beta then.
Be described in detail
Catalyst system component
Metallocenes
Here employed term ＂ metallocenes ＂ is often referred to by formula Cp
mMR
nX
qThe compound of expression, wherein Cp is can substituted cyclopentadienyl rings, or derivatives thereof, this derivative also can be substituted, and M is 4,5 or 6 group 4 transition metal, for example titaniums, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten, R are alkyl or the-oxyls with 1-20 carbon atom, and X is halogen and m=1-3, n=0-3, q=0-3, and the summation of m+n+q equals the oxidation state of transition metal.
The method of preparation and use metallocenes is well-known in the art.For example metallocenes is described in detail in US patent 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; 5,350,723; With 5,391,790, all be incorporated herein for reference separately.
Preferred metallocenes is those that are expressed from the next:
Wherein M is the metal of the periodic table of elements 4,5 or 6 families, zirconium preferably, hafnium and titanium, most preferably zirconium;
R
1And R
2Identical or different, preferably identical, and be a kind of in the following group: hydrogen atom, C
1-C
10Alkyl, preferred C
1-C
3Alkyl, C
1-C
10Alkoxyl group, preferred C
1-C
3Alkoxyl group, C
6-C
10Aryl, preferred C
6-C
8Aryl, C
6-C
10Aryloxy, preferred C
6-C
8Aryloxy, C
2-C
10Alkenyl, preferred C
2-C
4Alkenyl, C
7-C
40Aralkyl, preferred C
7-C
10Aralkyl, C
7-C
40Alkaryl, preferred C
7-C
12Alkaryl, C
8-C
10Aromatic yl alkenyl, preferred C
8-C
12Aromatic yl alkenyl, or halogen atom, preferred chlorine;
R
3And R
4It is hydrogen atom;
R
5And R
6Identical or different, preferably identical, and be a kind of in the following group: halogen atom, preferred fluorine, chlorine or bromine atom, C
1-C
10Alkyl, preferred C
1-C
4Alkyl, this alkyl can be by halogenation, C
6-C
10Aryl, this aryl can be by halogenation, preferred C
6-C
8Aryl, C
2-C
10Alkenyl, preferred C
2-C
4Alkenyl, C
7-C
40-aralkyl, preferred C
7-C
10Aralkyl, C
7-C
40Alkaryl, preferred C
7-C
12Alkaryl, C
8-C
40Aromatic yl alkenyl, preferred C
8-C
12Aromatic yl alkenyl ,-NR
15 2,-SR
15,-OR
15,-OSiR
15 3Or-PR
15 2Group, wherein R
15Be halogen atom, preferred chlorine atom, C
1-C
10Alkyl, preferred C
1-C
3Alkyl, or C
6-C
10Aryl, preferred C
6-C
9A kind of in the aryl;
-B(R
11)-,-(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 and be hydrogen atom, halogen atom, C
1-C
20Alkyl, preferred C
1-C
10Alkyl, C
1-C
20Fluoroalkyl, preferred C
1-C
10Fluoroalkyl, C
6-C
30Aryl, preferred C
6-C
20Aryl, C
6-C
30Fluorinated aryl, preferred C
6-C
20Fluorinated aryl, C
1-C
20Alkoxyl group, preferred C
1-C
10Alkoxyl group, C
2-C
20Alkenyl, preferred C
2-C
10Alkenyl, C
7-C
40Aralkyl, preferred C
7-C
20Aralkyl, C
8-C
40Aromatic yl alkenyl, preferred C
8-C
22Aromatic yl alkenyl, C
7-C
40Alkylaryl, preferred C
7-C
20Alkylaryl or R
11And R
12, or R
11And R
13Can form member ring systems with the atom that connects them;
M
2Be silicon, germanium or tin, preferred silicon or germanium, most preferably silicon;
R
8And R
9Identical or different and have a R
11Meaning;
M and n are identical or different and be 0,1 or 2, and preferred 0 or 1, m+n is 0,1 or 2, preferred 0 or 1; With
Radicals R
10Identical or different and have for R
11, R
12And R
13Given meaning.Two adjacent R
10The group formation member ring systems that can interconnect preferably contains the member ring systems of 4-6 carbon atom.
Alkyl refers to the straight or branched substituting group.Halogen (halo) refers to fluorine, chlorine, bromine or iodine atom, preferred fluorine or chlorine.
Particularly preferred metallocenes is structural formula (A) and compound (B):
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
12Has above meaning.
These chiral metals are luxuriant can be used for preparation height isotactic polypropylene copolymer by racemoid.Also might use pure R or S form.The optically active polymkeric substance can enough these pure stereoisomeric forms in any ratio prepare.Preferably the meso-form of metallocenes is removed to guarantee that center (being atoms metal) provides the stereospecific polyreaction.The separation of steric isomer can be finished by known technical literature.For special product, also might use outer/inner mixture.
In general, these metalloceness can prepare by multistep processes, introduce bridge and central atom comprising deprotonation repeatedly/metal replacement of aromatic ligand with by their halogen derivative.Following reaction mechanism is used to illustrate this universal method:
The addition method of preparation metallocenes fully is described in " (organometallic chemistry magazine ", 288 volumes (1985), and among 63-67 page or leaf and the EP-A-320762, it is for reference that the both is introduced into this paper.
Illustrative but the example of nonrestrictive preferred metallocenes comprise:
Two (2-methyl-4-phenyl-1-indenyl) ZrCl of dimethylsilane two bases
2
Two (2-methyl-4, the 5-benzo indenyl) ZrCl of dimethylsilane two bases
2
Two (2-methyl-4, the 6-di-isopropyl indenyl) ZrCl of dimethylsilane two bases
2
Two (2-ethyl-4-phenyl-1-indenyl) ZrCl of dimethylsilane two bases
2
Two (2-ethyl-4-naphthyl-1-indenyl) ZrCl of dimethylsilane two bases
2
Two (2-methyl-4-phenyl-1-indenyl) ZrCl of phenyl (methyl) silane two bases
2
Two (2-methyl-4-(1-the naphthyl)-1-indenyl) ZrCl of dimethylsilane two bases
2
Two (2-methyl-4-(2-the naphthyl)-1-indenyl) ZrCl of dimethylsilane two bases
2
Two (2-methyl-indenyl) ZrCl of dimethylsilane two bases
2
Two (2-methyl-4, the 5-di-isopropyl-1-indenyl) ZrCl of dimethylsilane two bases
2
Two (2,4, the 6-trimethylammonium-1-indenyl) ZrCl of dimethylsilane two bases
2
Two (2-methyl-4, the 6-7 sec.-propyl-1-indenyl) ZrCl of phenyl (methyl) silane two bases
2,
Two (2-methyl-4, the 6-di-isopropyl-1-indenyl) ZrCl of ethylene
2,
1, two (2-methyl-4, the 6-di-isopropyl-1-indenyl) ZrCl of 2-butylidene
2,
Two (2-methyl-4-ethyl-1-indenyl) ZrCl of dimethylsilane two bases
2,
Two (the 2-methyl 4-sec.-propyl-1-indenyl) ZrCl of dimethylsilane two bases
2,
Two (the 2-methyl-4-tertiary butyl-1-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2-methyl-4-sec.-propyl-1-indenyl) ZrCl of phenyl (methyl) silane two bases
2,
Two (2-ethyl-4-methyl isophthalic acid-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2, the 4-dimethyl-1-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2-methyl-4-ethyl-1-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2-methyl-α-acenaphthenyl (the acenaphth)-1-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2-methyl-4, the 5-phendioxin-indenyl) ZrCl of phenyl (methyl) silane two bases
2,
Two (2-methyl-4,5-(methyl the benzo)-1-indenyl) ZrCl of phenyl (methyl) silane two bases
2,
Two (2-methyl-4,5-(tetramethyl-the benzo)-1-indenyl) ZrCl of phenyl (methyl) silane two bases
2,
Two (2-methyl-α-acenaphthenyl-1-indenyl) ZrCl of phenyl (methyl) silane two bases
2,
Two (2-methyl-4, the 5-phendioxin-indenyl) ZrCl of ethylene
2,
1, two (2-methyl-4, the 5-phendioxin-indenyl) ZrCl of 2-butylidene
2,
Two (2-methyl-4, the 5-phendioxin-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2,4, the 7-trimethylammonium-1-indenyl) ZrCl of ethylene
2,
Two (2-methyl isophthalic acid-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2-methyl-l-indenyl) ZrCl of ethylene
2,
Two (2-methyl isophthalic acid-indenyl) ZrCl of phenyl (methyl) silane two bases
2,
Two (2-methyl isophthalic acid-indenyl) ZrCl of diphenyl silane two bases
2,
1, two (2-methyl isophthalic acid-indenyl) ZrCl of 2-butylidene
2,
Two (2-ethyl-1-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2-methyl-5-isobutyl--1-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2-methyl-5-isobutyl--1-indenyl) ZrCl of phenyl (methyl) silane two bases
2,
Two (the 2-methyl-5-tertiary butyl-1-indenyl) ZrCl of dimethylsilane two bases
2,
Two (2,5, the 6-trimethylammonium-1-indenyl) ZrCl of dimethylsilane two bases
2, or the like.
These preferred metallocene catalyst components are described in detail in U.S. patent 5,145,819; 5,243,001; 5,239,022; 5,329,033; 5,296,434; 5,276,208; With 5,374,752; And EP 549900 and 576970, all be incorporated herein for reference.
Activator
Metallocenes generally is used in combination with the activator of some forms, in order that produce active catalyst system.Term " activator " is defined as strengthening one or more metalloceness at this paper makes olefinic polymerization become any compound or the component of polyolefinic ability or the mixture of this compounds or component.For the present invention, alkylaluminoxane is preferably used as activator, most preferable aikyiaiurnirsoxan beta (MAO).In general, alkylaluminoxane contains 5-40 following repeating unit: for linear aikyiaiurnirsoxan beta:
With for the ring-type aikyiaiurnirsoxan beta:
Wherein R is the C that comprises mixed alkyl
1-C
8Alkyl.Particularly preferably being wherein, R is the compound of methyl.Aluminoxanes solution, especially methylaluminoxane solution can obtain from the solution form of supplier there with various concentration.Many methods that prepare aikyiaiurnirsoxan beta are arranged, and its nonrestrictive example is described in U.S. patent 4,665,208,4,952,540,5,091,352,5,206,199,5,204,419,4,874,734,4,924,018,4,908,463,4,968,827,5,308,815,5,329,032,5,248,801,5,235,081,5,157,137,5,103,031 and EP-A-0561476, EP-B1-0279586, EP-A-0594-218 and WO94/10180 all are incorporated herein for reference separately.(except as otherwise noted, otherwise this paper employed " solution " refers to any mixture, comprises suspension.)
Solid support material
The solid support material of Shi Yonging porousness granulated material preferably in the method for the invention, for example, talcum, inorganic oxide, butter and arborescens material such as polyolefine or polymerizable compound.
Most preferred solid support material is the porous inorganic oxide material, and they comprise in the periodic table of elements 2,3,4,5, the oxide compound of 13 or 14 family's metals.Silica, aluminum oxide, silica-alumina and its mixture are particularly preferred.Can use separately or mix other inorganic oxide that uses with silica, aluminum oxide or silica-alumina is magnesium oxide, titanium dioxide, zirconium white etc.
Preferably, solid support material is the porousness silica, and its surface-area is 10-700m
2/ g, total pore size volume are that 0.1-4.0cc/g and median size are in the 10-500 mu m range.More preferably, surface-area is at 50-500m
2In/g the scope, volume of voids in the 0.5-3.5cc/g scope and median size in the 20-200 mu m range.Most preferably, surface-area is at 100-400m
2In/g the scope, volume of voids be in the 0.8-3.0cc/g scope and median size in the 30-100 mu m range.The mean pore size of typical porous carrier material is in 10-1000 dust scope.The mean pore size of preferred employed solid support material is 50-500 dust and 75-350 dust most preferably.Particularly preferably be silica was dewatered 3-24 hour down at 100-800 ℃.
The method for preparing catalyst system
Method outstanding behaviours of the present invention is used aliphatic hydrocarbon solvent in the preparation process at catalyst system.Astoundingly, resulting catalyst system is compared with the metallocene catalyst system that makes usually and is had the activity that significantly improves.
Preferably, the aliphatic hydrocrbon that is used to prepare catalyst system is at least 1: 1 with the ratio of the cumulative volume of aromatic hydrocarbon, more preferably 1: 1-10: in 1 scope or higher, even more preferably 2: 1-8: 1, particularly 3: 1-5: 1.
The mixture of any aliphatic hydrocrbon or aliphatic hydrocrbon can be used in the method for the present invention.Aliphatic hydrocrbon is C preferably
3-C
10Alkane.More preferably, aliphatic hydrocrbon is selected from pentane, hexane, heptane, iso-pentane, hexanaphthene, octane, Trimethylmethane, butane, and propane.Most preferably, aliphatic hydrocrbon is selected from iso-pentane, pentane, hexane, heptane and Trimethylmethane.
Aikyiaiurnirsoxan beta typically is dissolved in the toluene as 10%-30% solution form.The preferred aikyiaiurnirsoxan beta of using, 30% solution of preferable methyl aikyiaiurnirsoxan beta is so that the volume of toluene reaches minimum.Under higher aikyiaiurnirsoxan beta concentration, trend towards forming gel.
Metallocenes can contact with carrier independently with aikyiaiurnirsoxan beta, and wherein metallocenes or aikyiaiurnirsoxan beta can at first contact with carrier, perhaps these three kinds of components can mixed once together.Same aliphatic hydrocarbon solvent can contact with three kinds of components or contact with any mixture of these three kinds of components individually.Therefore, precipitation can be under the situation that carrier exists, and before carrier contacts, or carries out after one or more of these components have been stated from the carrier.Yet preferably, metallocenes contacts in aromatic hydrocarbon solvent in advance with aikyiaiurnirsoxan beta, and their reaction product is mixed with carrier then.This is particularly preferred when having only metallocenes to be insoluble to or to be slightly soluble in aliphatic series and the aromatic hydrocarbon.Also preferably allow the metallocenes be to contact in the aromatic hydrocarbon solution (as toluene) at solution with aikyiaiurnirsoxan beta.Aliphatic hydrocrbon preferably mixes with solid support material, and metallocenes/alumoxane reaction product solution mixes under the sedimentary condition of generation with carrier then.
In another embodiment, be used to make metallocenes activatory aikyiaiurnirsoxan beta total amount to be divided into about equally two portions.First part and metallocenes react in solution and form reaction product, mix with the slurry of solid support material in aliphatic hydrocrbon then.Add the aikyiaiurnirsoxan beta of second section then.
No matter use above-mentioned which kind of method, in case all catalyst components mixing, if form slurry, the then easier mixing of mixture.Yet,, preferably use the least possible total liquid in order to help drying.Therefore, when using porous carrier material, the cumulative volume that preferably imposes on the liquid (aromatics and aliphatic hydrocrbon) of carrier is lower than 5 times of total pore size volume of porous carrier, more preferably less than 4 times of the total pore size volume of porous carrier with even more preferably less than 3 times of the total pore size volume of porous carrier.The method of measuring the total pore size volume of porous carrier is well-known in the prior art.Preferable methods is described in " experimental technique in the catalyst research " the 1st volume, AcademicPress, and nineteen sixty-eight is in the 67-96 page or leaf.
In preferred embodiments, metallocenes contact in advance with activator and in solution reaction time of 1 minute-16 hours, more preferably at least 10 minutes and most preferably 10 minutes-1 hour.Equally, preferably metallocenes/alumoxane reaction product is mixed with the hexane slurry of solid support material, and allow mixture leave standstill at least 10 minutes, preferred 10 minutes-1 hour.If aikyiaiurnirsoxan beta is divided into several parts, then preferably allow second section and metallocenes/aikyiaiurnirsoxan beta/solid support material mixture reaction at least 10 minutes again, preferred 10 minutes-1 hour.
In case after comprising that all components of aliphatic hydrocrbon mixes, catalyst system preferably is dried, though catalyst system can be directly used in the polyreaction.If catalyzer is dried or allows drying, then seldom be heated or do not heat.Drying conditions depends on specific embodiment accurately, the size of batch of catalyst and the amount of liquid, but in each case preferably in the least possible time not half ground heat or do not heat.The purging of vacuum or rare gas element such as nitrogen can use, but preferably uses these only to avoid polluting reduction with catalyst activity once more.
The supported catalyst system can be directly used in polyreaction or catalyst system and can use in the prior art well-known method to carry out prepolymerization.For the details of prepolymerization reaction, referring to US patent 4,923,833 and 4,921,825, EP0279863 and EP0354893, it is for reference that wherein each part is introduced into this paper.
In another embodiment, catalyst system is by using alkene promotor to prepare as the metallocenes reaction reagent.This method is also found to cause to improve active by the inventor, described in unexamined US patent application No.____ (" improved metallocene catalyst system " applying for that with the application it is for reference to be incorporated herein this paper by same contriver on the same day).
Polyreaction and catalyst system performance
The polyreaction that can in any method that comprises gas phase, slurry or solution phase or autoclave processes, be used for the comonomer of any monomer and arbitrariness use by the catalyst system of method preparation of the present invention.(unless different indications are arranged, and employed here " polyreaction " comprises that copolymerization and " monomer " comprise comonomer).Preferably, use gas phase or slurry phase process, most preferably use body liquid propylene polymerization process.
In preferred embodiments, the present invention relates to propylene or ethene (especially propylene) body liquid-phase polymerization and the copolymerization in slurry or gas phase polymerization process (especially slurry phase polymerisation process).Another embodiment relates to propylene or ethene (especially propylene) have alpha-olefin comonomer such as the 'alpha '-olefin monomers class of 4-20 carbon atom (preferred 4-12 carbon atom) such as ethene, butene-1, amylene-1,4-methylpentene-1, hexene-1, octene-1, decylene-1 and cyclic olefin such as vinylbenzene, cyclopentenes or norbornylene with one or more copolymerization.Other suitable monomers comprises polar vinyl, alkadiene such as dienes, 1,3-butadiene for example, 1,4-hexadiene, norbornadiene or vinyl norbornene, acetylene and aldehyde monomer.
In another embodiment, ethene or propylene and at least two kinds of different copolymer monomers carry out polyreaction and form terpolymer etc., preferred comonomer is to have 3-10 carbon atom, the more preferably 'alpha '-olefin monomers of 3-8 carbon atom, and/or have 4-10 carbon atom diene mixture.
Typically, use circulation continuously in gas phase polymerization process, wherein in the round-robin part of this reactor, circulating current (being known as recirculation flow or fluidizing medium in addition) heats in reactor by heat of polymerization.Recirculation flow usually contains one or more and come continuous recycled monomer by the fluidized-bed that has catalyzer to exist under reaction conditions.Cooling system by the reactor outside is removed this heat in round-robin another part.Recirculation flow is discharged from fluidized-bed and recirculation is returned in the reactor.Simultaneously, polymer product is discharged from reactor, adds new or fresh monomer then and replaces institute's polymeric monomer.(for example referring to US patent 4,543,399,4,588,790,5,028,670,5,352,749,5,405,922 and 5,436,304, it is for reference that it all is introduced into this paper)
Slurry phase polymerisation process generally uses 1-500 normal atmosphere or even the temperature of higher pressure and-60 ℃-280 ℃.In slurry polymerization, the suspension of solid particulate polymkeric substance forms in liquid polymerizaton medium, in medium with ethene and comonomer and also have hydrogen to join usually with catalyzer.Employed liquid for example is alkane or naphthenic in polymerisation medium.Employed medium should be liquid and comparison inert under polymerizing condition.The non-limitative example of liquid medium comprises hexane and Trimethylmethane.
Shown in following embodiment, catalyst system of the present invention demonstrates the activity that the metallocene catalyst system on the carrier that makes than usual significantly improves.Active any raising is the height ideal in commercial run.
The polymkeric substance and the multipolymer that are made by catalyst system of the present invention can be used in the forming operation, for example film, sheet material and fiber extrusion molding and co-extrusion and blowing, injection moulding, sheet heat forming and rotational moulding.Film comprises the inflation or the casting films of the single or multiple lift structure formation that forms by co-extrusion or by laminating method.This type of film material can contact with non-food product in the application in Food Contact and be used as shrinkable film, from mucous membrane, and Elastic Film, film for sealing, oriented film, snack packing bag, weight package pack, groceries bag, baking and Frozen Food Packaging, medical package, industrial liner, film material etc.The fiberizing operation comprises melt-spinning, solvent spinning and the operation of melt-blown fiber.This fibrid can be used to make filter material with woven or non-woven form, diaper fabric, medical clothes, geotextile (geotextile) etc.Extruded product comprises, for example, medical pipe, wire rod and cable coating, the geotechnique is with film and sump liner.Moulded parts comprises the single or multiple lift structure, and its form is a bottle, jar, big hollow piece, rigid food product containers and toy etc.
Embodiment
Embodiment 1
10g silica gel (Davison D-948, median size, " APS " ,=35m, dry down at 600 ℃) join in 8 ounces of bottles that magnetic stirring bar is housed.In bottle, add the 40ml hexane.In 4 ounces of bottles that magnetic stirring bar is housed, add 0.11g racemize-Me
2Si (2-Me-4-phenyl indenyl)
2ZrCl
2With the solution (30wt%) of 5ml methylaluminoxane (" MAO ") in toluene.Mixture at room temperature stirred 10 minutes.Mixture is transferred in 8 ounces of bottles that contain silica gel and hexane slurry then.This mixture at room temperature reacted 10 minutes.6.4mlMAO the solution in toluene (30wt%) is added in the bottle, mixture at room temperature reacted 10 minutes then.After reaction finished, mixture came in addition dry under 40 ℃-50 ℃ with nitrogen purging.The mobile solid gains freedom after preparation process finishes.
Rise the solution (1.5M) of adding 0.3ml triethyl aluminum in heptane in the autoclave pressure to clean 2-, add 1 liter of liquid propene subsequently.Reactor is heated to 70 ℃.By the catalyzer injection tube catalyzer for preparing more than the 100mg is joined in the autoclave pressure.By the 200ml liquid propene with catalyst detergent in autoclave pressure.Stagnation pressure is about 480psig in the reactor.Polyreaction was carried out under 70 ℃ 1 hour.After polyreaction, unreacted propylene is drawn out of, and polymer slurries is transferred in the evaporating pan.Autoclave pressure inwall and agitator clean very much.Obtain 294g polymkeric substance altogether.
Embodiment 2
Repeat embodiment 1, just in this preparation process, use 0.2g racemize-Me
2Si (2-Me-4-phenyl indenyl)
2ZrCl
2Obtain 187g polymkeric substance altogether.
Embodiment 3
Repeat embodiment 1, just beginning all 11.4ml MAO to be mixed with metallocenes and do not add subsequently MAO.Obtain 199g polymkeric substance altogether.
Embodiment 4
Repeat embodiment 3, just in this preparation process, use 0.2g racemize-Me
2Si (2-Me-4-phenyl indenyl)
2ZrCl
2Obtain 169g polymkeric substance altogether.
Embodiment 5 (contrast)
10g silica gel (Davison D-948, median size, " APS " ,=35m, dry down at 600 ℃) join in 8 ounces of bottles that magnetic stirring bar is housed.In 4 ounces of bottles that magnetic stirring bar is housed, add 0.11g racemize-Me
2Si (2-Me-indenyl)
2ZrCl
2With the solution (30wt%) of 11.4ml methylaluminoxane (" MAO ") in toluene.Mixture at room temperature stirred 10 minutes.The 30ml toluene solvant is added in the mixture, and mixture is transferred in 8 ounces of bottles that contain silica gel then.This mixture at room temperature reacted 10 minutes.6.4ml the solution (30wt%) of MAO in toluene is added in the bottle, mixture at room temperature reacted 10 minutes then.After reaction finished, mixture came in addition dry under 40 ℃-50 ℃ with nitrogen purging.The mobile solid gains freedom after preparation process finishes.Polymerization process according to embodiment 1 obtains 160g polymkeric substance altogether.
Embodiment 6
10g silica gel (Davison D-948, median size, " APS " ,=35m, dry down at 600 ℃) join in 8 ounces of bottles that magnetic stirring bar is housed.Add the 40ml hexane to bottle.In 4 ounces of bottles that magnetic stirring bar is housed, add 0.2g racemize-Me
2Si (2-Me-4-phenyl indenyl)
2ZrCl
2With the solution (30wt%) of 11.4ml methylaluminoxane (" MAO ") in toluene.Mixture at room temperature stirred 10 minutes.Mixture is transferred in 8 ounces of bottles that contain silica gel and hexane slurry then.This mixture at room temperature reacted 10 minutes.0.5ml vinylbenzene (99%) is added in the bottle, mixture at room temperature reacted 10 minutes then.After reaction finished, mixture came in addition dry under 40 ℃-50 ℃ with nitrogen purging.The mobile solid gains freedom after preparation process finishes.Polymerization process according to embodiment 1 obtains 232g polymkeric substance altogether.
Embodiment 7
10g silica gel (Davison D-948, median size, " APS " ,=35m, dry down at 600 ℃) join in 8 ounces of bottles that magnetic stirring bar is housed.Add the 40ml hexane to bottle.In 4 ounces of bottles that magnetic stirring bar is housed, add 0.2g racemize-Me
2Si (2-Me-4-phenyl indenyl)
2ZrCl
2With the solution (30wt%) of 5ml methylaluminoxane (" MAO ") in toluene.Mixture at room temperature stirred 10 minutes.Mixture is transferred in 8 ounces of bottles that contain silica gel and hexane slurry then.This mixture at room temperature reacted 10 minutes.6.4ml the solution (30wt%) of MAO in toluene is added in the bottle, mixture at room temperature reacted 10 minutes.0.5ml vinylbenzene (99%) is added in the bottle, mixture at room temperature reacted 10 minutes then.After reaction finished, mixture came in addition dry under 40 ℃-50 ℃ with nitrogen purging.The mobile solid gains freedom after preparation process finishes.Polymerization process according to embodiment 1 obtains 240g polymkeric substance altogether.
Although described and illustrated the present invention with reference to specific embodiment, those of ordinary skill will recognize that in the art, and the present invention itself has many difference variations that do not have explanation here.For these reasons, should be only referring to claims of determining true scope of the present invention.
Though appended claim has simple contact according to patent practice, each feature of any one can combine with each feature of other claims or main claim in claims.
Claims (10)
1, a kind of method that forms the metallocene catalyst system on the carrier, it comprises:
(a) allow the reaction of one or more metalloceness and alumoxane activator form catalyst solution and
(b) allow catalyst solution in the presence of aliphatic hydrocrbon, mix with solid support material.
2, a kind of method that forms the metallocene catalyst system on the carrier, it comprises:
(a) allow the reaction of metallocenes and alumoxane activator form catalyst solution,
(b) allow aliphatic hydrocrbon mix with solid support material and
(c) allow catalyst solution mix with mixture.
3, a kind of method that forms the metallocene catalyst system on the carrier, it comprises:
(a) allow metallocenes and first part's aikyiaiurnirsoxan beta reaction form catalyst solution,
(b) allow aliphatic hydrocrbon and solid support material mix the formation mixture,
(c) allow catalyst solution mix and then with mixture
(d) activator of interpolation second section.
4, the method for any one in the aforementioned claim, wherein catalyst solution comprise aromatic hydrocarbon solvent and wherein the ratio of aliphatic hydrocrbon and aromatic hydrocarbon be at least 1: 1.
5, the method for any one in the aforementioned claim, wherein metallocenes is expressed from the next:
Wherein M is selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten;
R
1And R
2Identical or different, and be a kind of in the following group: hydrogen atom, C
1-C
10Alkyl, preferred C
1-C
3Alkyl, C
1-C
10Alkoxyl group, C
6-C
10Aryl, C
6-C
10Aryloxy, C
2-C
10Alkenyl, preferred C
2-C
4Alkenyl, C
7-C
40Aralkyl, C
7-C
40Alkaryl, C
8-C
40Aromatic yl alkenyl, or halogen atom;
R
3And R
4It is hydrogen atom;
R
5And R
6Identical or different, and be a kind of in the following group: halogen atom, C
1-C
10Alkyl, this alkyl can be by halogenation, C
6-C
10Aryl, this aryl can be by halogenation, C
2-C
10Alkenyl, C
7-C
40-aralkyl, C
7-C
40Alkaryl, C
8-C
40Aromatic yl alkenyl ,-NR
15 2,-SR
15,-OR
15,-OSiR
15 3Or-PR
15 2Group, wherein R
15Be halogen atom, C
1-C
10Alkyl, or C
6-C
10A kind of in the aryl;
R
7Be
-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 and be hydrogen atom, halogen atom, C
1-C
20Alkyl, C
1-C
20Fluoroalkyl, C
6-C
30Aryl, C
6-C
30Fluorinated aryl, C
1-C
20Alkoxyl group, C
2-C
20Alkenyl, C
7-C
40Aralkyl, C
8-C
40Aromatic yl alkenyl, C
7-C
40Alkaryl, or R
11And R
12, or R
11And R
13Can form member ring systems with the atom that connects them;
M
2Be silicon, germanium or tin;
R
8And R
9Identical or different and have a R
11Meaning;
M and n are identical or different and be 0,1 or 2, and m+n is 0,1 or 2; With
Radicals R
10Identical or different and have for R
11, R
12And R
13Given meaning, two adjacent R
10The group formation member ring systems that can interconnect.
6, the method for any one in the aforementioned claim, wherein aliphatic hydrocrbon is C
3-C
10Paraffinic hydrocarbons.
7, the method for any one in the aforementioned claim further comprises the step that reclaims the metallocene catalyst system on the exsiccant carrier.
8, the method for any one in the aforementioned claim, wherein aliphatic hydrocrbon is iso-pentane or hexane, solid support material is that silica and activator are methylaluminoxane.
9, the method for any one in the aforementioned claim, wherein metallocenes is selected from racemic:
Two (the 2-methyl indenyl) zirconium dichlorides of dimethylsilane two bases;
Two (2, the 4-dimethyl indenyl) zirconium dichlorides of dimethylsilane two bases;
Two (2,5, the 6-trimethylammonium indenyl) zirconium dichlorides of dimethylsilane two bases;
The two indenyl zirconium dichlorides of dimethylsilane two bases;
Two (4,5,6, the 7-tetrahydro indenyl) zirconium dichlorides of dimethylsilane two bases;
Two (2-methyl-4, the 5-benzo indenyl) zirconium dichlorides of dimethylsilane two bases;
Two (2-methyl-4-phenyl indenyl) zirconium dichlorides of dimethylsilane two bases;
Two (2-methyl-4, the 6-di-isopropyl indenyl) zirconium dichlorides of dimethylsilane two bases;
Two (2-methyl-4-naphthyl indenyl) zirconium dichlorides of dimethylsilane two bases; With
Two (2-ethyl-4-phenyl indenyl) zirconium dichlorides of dimethylsilane two bases.
10, the metallocene catalyst system that makes by the method for any one in the aforementioned claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2664496P | 1996-09-24 | 1996-09-24 | |
| US60/026,644 | 1996-09-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1231678A true CN1231678A (en) | 1999-10-13 |
Family
ID=21833023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97198171A Pending CN1231678A (en) | 1996-09-24 | 1997-08-19 | Improved method for preparing supported metallocene catalyst system |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0928297A1 (en) |
| JP (1) | JP2001500921A (en) |
| KR (1) | KR20000048478A (en) |
| CN (1) | CN1231678A (en) |
| CA (1) | CA2263081A1 (en) |
| TW (1) | TW367339B (en) |
| WO (1) | WO1998013393A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101010705B (en) * | 2004-07-08 | 2011-03-23 | 埃克森美孚化学专利公司 | Polymer production at supercritical conditions |
| CN112409515A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Preparation method of metallocene polypropylene catalyst |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0017547D0 (en) * | 2000-07-17 | 2000-09-06 | Bp Chem Int Ltd | Supported polymerisation catalysts |
| US6720396B2 (en) | 2000-11-30 | 2004-04-13 | Univation Technologies, Llc | Polymerization process |
| US20020137861A1 (en) * | 2000-12-04 | 2002-09-26 | Woo Min Song | Polymerization process |
| MX2009004201A (en) * | 2006-10-19 | 2009-07-15 | Ct De Investigacion En Quimica | Catalyst for the heterogeneous phase polymerisation of conjugated dienes and olefins, method for obtaining same and use thereof. |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| FI112233B (en) * | 1992-04-01 | 2003-11-14 | Basell Polyolefine Gmbh | Catalyst for olefin polymerization, process for its preparation and its use |
| US5240894A (en) * | 1992-05-18 | 1993-08-31 | Exxon Chemical Patents Inc. | Method for making and using a supported metallocene catalyst system |
| CA2163789C (en) * | 1993-05-25 | 2006-10-24 | Terry John Burkhardt | Supported metallocene catalyst systems for the polymerization of olefins, preparation and use thereof |
| FI96866C (en) * | 1993-11-05 | 1996-09-10 | Borealis As | Support olefin polymerization catalyst, its preparation and use |
| AU685649B2 (en) * | 1994-06-24 | 1998-01-22 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
| US5763543A (en) * | 1994-09-14 | 1998-06-09 | Exxon Chemical Patents Inc. | Olefin polymerization process with little or no scavenger present |
-
1997
- 1997-08-19 KR KR1019990702347A patent/KR20000048478A/en not_active Application Discontinuation
- 1997-08-19 WO PCT/US1997/014533 patent/WO1998013393A1/en not_active Application Discontinuation
- 1997-08-19 CA CA002263081A patent/CA2263081A1/en not_active Abandoned
- 1997-08-19 EP EP97936513A patent/EP0928297A1/en not_active Withdrawn
- 1997-08-19 JP JP10515637A patent/JP2001500921A/en active Pending
- 1997-08-19 CN CN97198171A patent/CN1231678A/en active Pending
- 1997-09-08 TW TW086112949A patent/TW367339B/en active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101010705B (en) * | 2004-07-08 | 2011-03-23 | 埃克森美孚化学专利公司 | Polymer production at supercritical conditions |
| CN112409515A (en) * | 2019-08-23 | 2021-02-26 | 中国石油化工股份有限公司 | Preparation method of metallocene polypropylene catalyst |
| CN112409515B (en) * | 2019-08-23 | 2023-10-20 | 中国石油化工股份有限公司 | Preparation method of metallocene polypropylene catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0928297A1 (en) | 1999-07-14 |
| JP2001500921A (en) | 2001-01-23 |
| WO1998013393A1 (en) | 1998-04-02 |
| CA2263081A1 (en) | 1998-04-02 |
| TW367339B (en) | 1999-08-21 |
| KR20000048478A (en) | 2000-07-25 |
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