CN1284805C

CN1284805C - Solid, particulated, spray dried, heterogenous catalyst composition

Info

Publication number: CN1284805C
Application number: CN 03811156
Authority: CN
Inventors: J·A·库克; A·M·舍伯-沃尔特斯
Original assignee: Univation Technologies LLC
Current assignee: Univation Technologies LLC
Priority date: 2002-06-03
Filing date: 2003-05-22
Publication date: 2006-11-15
Anticipated expiration: 2023-05-22
Also published as: CA2482640A1; AU2003233649B2; JP2005526175A; AU2003233649A1; CN1653093A; BR0311438A; WO2003102037A1; EP1509552A1

Abstract

A solid, particulated, heterogeneous, spray-dried, catalyst composition for the polymerization of addition polymerizable monomers comprising: a) a Group 4 metallocene compound; b) a solid Group 4 metal-magnesium halide complex comprising moieties of at least magnesium, a Group 4 transition metal, and a halide; c) finely divided, inert filler, and d) an optional binder capable of joining components a) and b) and optionally c) into a particulated, heterogeneous, agglomerate without adversely affecting the catalytic properties thereof, and a method for the manufacture thereof comprising forming a mixture of the above composition in a liquid diluent and spray-drying the same to remove diluent.

Description

The spray-dired multiphase catalyst composition of solid granular

Cross-reference statement

The application requires the US provisional application No.60/385 that declared on June 3rd, 2002,796 right of priority.

Background of the present invention

The present invention relates to the solid granular multiphase catalyst composition that comprises Z-N part and metallocenes part by the spray drying technology preparation.This catalyst composition can be used for producing polyolefine, especially by one or more alkene or diolefinic monomer polymerization under slurry or vapour phase polymerization condition.

The catalyst composition that comprises metallocene components, Z-N component and carrier is disclosed in US-A 5,747, and 405,5,539,076,5,395,810,5,266,544,5,183,867,4,659,685; EP-A 676,418,717,755,705,848,747,402; In WO98/02245,96/13532,95/13871.Optional spray-dired Ziegler-Natta catalyst that has filler such as a silica or metalloscene catalyst be by US-A 5,567, and 665,5,604,172,5,652,314,5,648,310,5,672,669 and 5,674,795 is disclosed.

General introduction of the present invention

Be used for the monomeric polymeric solid granular of addition polymerization multiphase catalyst composition but the invention provides, comprise:

A) 4 family's Metallocenic compounds;

B) contain magnesium at least, the solid 4 families metal-magnesium halide complex of 4 group 4 transition metals and halid structure division;

C) the particulate inert filler and

D) Ren Xuan binding agent, it can with component a) and b) and optional c) be combined into the heterogeneous agglomerate of particulate state, and do not have its catalytic performance of disadvantageous effect.

But the method that the present invention also provides preparation to be used for the monomeric polymeric solid granular of addition polymerization multiphase catalyst composition comprises forming the mixture that contains following component:

A) 4 family's Metallocenic compounds;

C) particulate inert filler;

D) Ren Xuan binding agent, it can with component a) and b) and optional c) be combined into the heterogeneous agglomerate of particulate state, and do not have its catalytic performance of disadvantageous effect; With

E) organic volatile liquid diluent;

And with this mixture spraying drying, so that remove thinner and the product that stays the solid agglomerated particle form.

But the present invention further provides the monomer that is used to produce addition polymerization, especially the polymkeric substance of alkene, the most especially the method for Alathon or multipolymer, comprise: allow ethene and optional high alpha-olefin monomer and/or diolefine under polymerizing condition with the catalyst according to the invention composition under gas phase or slurry polymerization conditions, in the presence of one or more active cocatalysts, contact ideally.With polymkeric substance by using independent catalyst component to form, or, generally have wide molecular weight and/or bimodal molecular weight distribution by the polymkeric substance that uses multiphase catalyst composition of the present invention to obtain by the formed polymer phase ratio of polymkeric substance of blend by the independent preparation of arbitrary component of this catalyst composition.

The accompanying drawing summary

Fig. 1 is the scanning-tunnelling electron photomicrograph (STEM) according to the representative particle of the solid granular multiphase catalyst composition of embodiment 4 preparations.

Detailed description of preferred embodiments

The all elements periodictable of being mentioned herein is meant the Press by CRC, Inc., the periodic table of elements of 1999 publication and acquisition of copyright.Also have, any family that is mentioned is the IUPAC system that is used for numbering family as use in the family that this periodic table of elements reflects.Implement for the ease of United States Patent (USP), any patent that this paper marks, patent application or publication are introduced for reference thus comprehensively, especially disclosing for the general knowledge of structure, synthetic technology and this area.Term when using for composition, mixture or method in this article " comprises " the other existence of not planning to get rid of any other compound, component or step.Term " aromatics " or " aryl " are meant polyatom, the cyclic rings system that contains (4 δ+2) π-electronics, and wherein δ is the integer more than or equal to 1.

As component 4 family's Metallocenic compounds a) are the Organometallic complexes that contain the structure division of at least one π-bonding that is connected with 4 family's metals.It is desirable to contain the zirconic metal complexes (zirconocene) of 1-3 π-bonding negatively charged ion or neutral ligand group (they can be the anion ligand groups of ring-type or acyclic delocalization π-bonding) especially.The anion ligand examples of groups of this type of π-bonding is a conjugation or non-conjugated, ring-type or non--cyclic diene base, allyl group, boron benzene (boratabenzene) group of mixing, phosphurane (phosphole), and aromatic hydrocarbon group.Term " π-bonding " is meant that ligand groups is bonded to transition metal by shared electronics from the part delocalized bond.

The group that each atom in the group of delocalization π-bonding can be independently be selected among following replaces: hydrogen, halogen, alkyl, the halo alkyl, the metalloid radicals that alkyl replaces, wherein this metalloid is selected from 14 families of the periodic table of elements, and is further contained this alkyl that the heteroatomic structure division of 15 or 16 families replaces-and the metalloid radicals of halo alkyl-replacement.Be included in term " alkyl " scope is C _1-20Straight chain, branching and cyclic alkyl, C _6-20Aromatic group, C _7-20The aromatic group of alkyl-replacement, and C _7-20The alkyl that aryl replaces.In addition, two or more these type of groups can form the condensed ring system together, comprise partially or completely halogenated condensed ring system, or they can form metallic ring (metallocycle) with metal.The organic quasi-metal group of suitable alkyl-replacement comprise the list of 14 family's elements-, two-and the three-organic quasi-metal group that replaces, wherein each hydrocarbyl group contains 1-20 carbon atom.The organic quasi-metal examples of groups of suitable alkyl-replacement comprises trimethyl silyl, triethylsilyl, ethyl dimetylsilyl, methyl diethylsilane base, triphenyl germane base and trimethylammonium germane base.The example that contains the 15 or 16 heteroatomic structure divisions of family comprises amine, phosphine, ether or sulfide based structural part or their divalent derivative, for example be bonded in transition metal or lanthanide series metal, and the acid amides that contains metalloid group, phosphide, ether or the sulfide group that are bonded in alkyl or alkyl replacement.

The examples of groups of suitable negatively charged ion delocalization π-bonding comprises cyclopentadienyl, indenyl, fluorenyl, tetrahydro indenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydro anthryl, six hydrogen anthryls, decahydro anthryl, phosphurane, with the assorted phenyl group of boron, and their alkyl-silyl-(comprise single-, two-, or three (alkyl) silyl is interior) derivative that replaces.Preferred anionic surfactants delocalization π-bonded group is a cyclopentadienyl, pentamethyl-cyclopentadienyl, tetramethyl-ring pentadienyl, tetramethyl-(trimethyl silyl)-cyclopentadienyl, indenyl, 2,3-dimethyl indenyl, fluorenyl, 2-methyl indenyl, 2-methyl-4-phenyl indenyl, tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydro indenyl.

The assorted benzene class of boron is the anion ligand that belongs to the boracic analogue of benzene.They are exactly known early in the art, are described in Organometallics by people such as G.Herberich, and 14,1, among the 471-480 (1995).The assorted benzene class of preferred boron is corresponding to following structural:

Wherein " be selected from alkyl, silyl, N, N-dialkyl amino, or germyl, this R " have 20 non-hydrogen atoms at the most to R.In the title complex of the divalent derivative that comprises this type of delocalization π-bonded group, the divalent group that its atom connects by covalent linkage or covalent linkage is bonded in another atom of this title complex, therefore forms the bridging system.

The phosphurane class is the anion ligand that belongs to phosphorated cyclopentadienyl analogue.They are exactly known early in the art, have been described in WO 98/50392 and other place.Preferred phosphurane part is corresponding to following structural:

" be selected from alkyl, silyl, N, N-dialkyl amino, or germyl, this R " have 20 non-hydrogen atoms and optional one or more R at the most " group can be connected to together, form the polycyclic fused ring system, or form the bridged group that is connected in this metal for R wherein.In the title complex of the divalent derivative of the group that comprises this type of delocalization π-bonding, the divalent group that its atom connects by covalent linkage or covalent linkage is bonded in another atom of this title complex, therefore forms the bridging system.

Phosphinimine/cyclopentadienyl complex compound is disclosed among the EP-A-890581, corresponding to structural formula [(R ^{* *}) ₃P=N] _bM ^*(Cp) (L ¹) _3-b, wherein:

R ^{* *}Be monovalent ligands, hydrogen for example, halogen, or alkyl, or two R ^{* *}Form the divalence part together,

M ^*Be 4 family's metals,

Cp is a cyclopentadienyl, or the group of similar delocalization π-bonding,

L ¹Be the monovalent ligands group, hydrogen for example, halogen or alkyl,

B is 1 to 3 numerical value; With

N is 1 or 2.

The catalyzer that one class is fit to is the transition metal complex corresponding to following structural:

Lp _tMX _mX ' _nX " _p, or its dipolymer, wherein:

Lp is and the group of the negatively charged ion delocalization π-bonding of M keyed jointing, contains 50 non-hydrogen atoms at the most, optional two Lp groups can in conjunction with, form bridged linkage and further optional Lp can be bonded in X;

M is+2 ,+3 or+4 family's metals of the periodic table of elements of 4 form oxidation state;

X is the optional divalent group that forms 50 non-hydrogen atoms at the most of the metallic ring with M with Lp;

X ' is the neutral ligand of choosing wantonly of 20 non-hydrogen atoms at the most that has;

" each has the monovalent anion structure division of 40 non-hydrogen atoms at the most to X naturally; randomly; " group can be with covalent bonding together for two X, formation has two valent divalence dianion structure divisions that are bonded in M, perhaps, optional 2 X " group can be with covalent bonding together; form the neutrality that is incorporated into M (so M is+2 oxidation state) with the π key; conjugation or non-conjugated diene hydrocarbon; or further optional one or more X " and one or more X ' groups can be bonded together, and form thus simultaneously with covalent bonds in M with utilize Lewis base functional group to be coordinated in the structure division of M;

T is 0,1 or 2;

M is 0 or 1;

N is 0 to 3 numerical value;

P is 0 to 3 integer; With

Summation t+m+p equals the form oxidation state of M, except when 2 X, and " group forms together with the π key and is incorporated into beyond the neutral conjugation or non-conjugated diene of M, and summation t+m equals the form oxidation state of M in this case.

Preferred complexes comprises those that contain one or two Lp group.A kind of title complex in back comprises those that contain the bridged group that connects two Cp groups.Preferred bridged group comprises corresponding to structural formula (ER ^* ₂) _x, B (NR ^* ₂), or B (NR ^* ₂) ₂, wherein E is a silicon, germanium, tin, or carbon, R ^*Independently be hydrogen separately or be selected from silyl, alkyl, the group in-oxyl and their binding substances, this R ^*Have at the most 30 carbon or Siliciumatom, R ^*Independently be to be selected from silyl separately, the group in alkyl and their binding substances, this R ^*Having at the most 30 carbon or Siliciumatom and x is 1 to 8.Preferably, R ^*Be methyl independently of one another, ethyl, propyl group, benzyl, butyl, phenyl, methoxyl group, oxyethyl group, or phenoxy group, and R ^*Be methyl, ethyl, propyl group, benzyl or butyl.

The example that contains the title complex of two Lp groups is the compound corresponding to following structural:

Wherein:

M is+2 or+titanium of 4 form oxidation state, zirconium or hafnium, preferred zirconium or hafnium;

R ³Be selected from hydrogen independently of one another, alkyl, silyl, germyl, cyano group, halogen and their binding substances, this R ³Have 20 non-hydrogen atoms at the most, or adjacent R ³Group forms divalent derivative (that is to say alkylene (hydrocarbadiyl), silicylene (siladiyl) or germanous alkyl (germadiyl)) together, therefore form the condensed ring system and

X " independently is the anion ligand group of 40 non-hydrogen atoms at the most; perhaps " group is formed up to the dianion ligand groups of many 40 non-hydrogen atoms to two X together separately, or be the conjugated diolefine that forms π-title complex with M together with 4 to 30 non-hydrogen atoms, therefore M be+2 form oxidation state and

R ^*, R ^*, E and x such as front define, preferred (ER ^* ₂) _xBe dimethylsilane two bases or ethylidene, and BNR ^* ₂Be two (sec.-propyl) amino borane, two bases.

Above-mentioned metal complexes is particularly suited for preparing the polymkeric substance with stereospecific molecular structure.In this type of function, preferably this title complex has C _sSymmetry or have chirality, the solid rigid structure.The example of the first kind is the system with different delocalization π-keyed jointing, such as the compound of a cyclopentadienyl and a fluorenyl.People such as Ewen, J.Am.Chem.Soc.110,6255-6256 (1980) discloses the Ti (IV) or the zirconium (IV) that are used to prepare the syndiotaxy olefin polymer and has been basic similar system.The example of chiral structure comprise racemize two-the indenyl title complex.People such as Wild, J.Organomet.Chem.232,233-47, (1982) disclose the similar system based on Ti (IV) or Zr (IV) that is used to prepare the isotaxy olefin polymer.

The example of bridgingligand that contains the group of two π-bondings is: two (cyclopentadienyl) silane of dimethyl, two (tetramethyl-ring pentadienyl) silane of dimethyl, two (the 2-ethyl cyclopentadiene-1-yl) silane of dimethyl, two (the 2-tertiary butyl cyclopentadiene-1-yl) silane of dimethyl, 2, two (tetramethyl-ring pentadienyl) propane of 2-, two (indenes-1-yl) silane of dimethyl, two (tetrahydroindene-1-yl) silane of dimethyl, two (fluorenes-1-yl) silane of dimethyl, two (tetrahydrochysene fluorenes-1-yl) silane of dimethyl, two (2-methyl-4-phenylindan-1-yl)-silane of dimethyl, two (the 2-methyl indenes-1-yl) silane of dimethyl, amino two (cyclopentadiene-1-yl) borine two bases of two (sec.-propyls), amino two (2-methyl-4-phenylindan-1-yl)-borine two bases of two (sec.-propyls), amino two (2-methyl indenes-1-yl) borine two bases of two (sec.-propyls), dimethyl (cyclopentadienyl) (fluorenes-1-yl) silane, dimethyl (cyclopentadienyl) (octahydro fluorenes-1-yl) silane, dimethyl (cyclopentadienyl) (tetrahydrochysene fluorenes-1-yl) silane, (1,1,2, the 2-tetramethyl-)-1, two (cyclopentadienyl) disilane of 2-, 1, two (cyclopentadienyl) ethane of 2-, and dimethyl (cyclopentadienyl)-1-(fluorenes-1-yl) methane.

Preferred X " group is selected from hydride ion, alkyl, silyl; germyl, halo alkyl, halo silyl; silyl alkyl and hydrocarbyl amino, or two X " group forms the divalent derivative of conjugated diolefine together, or they form the conjugated diolefine of neutral π-bonding together." group is C to most preferred X _1-20Alkyl.

Being suitable for the title complex (comprising the bridging title complex) that contains two Lp groups of the present invention comprising:

Dimethyl two (cyclopentadienyl) closes zirconium,

Dibenzyl two (cyclopentadienyl) closes zirconium,

Methyl-benzyl two (cyclopentadienyl) closes zirconium,

Aminomethyl phenyl two (cyclopentadienyl) closes zirconium,

Phenylbenzene two (cyclopentadienyl) closes zirconium,

Allyl group two (cyclopentadienyl) closes titanium,

Methyl methoxy base two (cyclopentadienyl) closes zirconium,

Chloromethyl two (cyclopentadienyl) closes zirconium,

Dimethyl two (pentamethyl-cyclopentadienyl) closes zirconium,

Dimethyl two (pentamethyl-cyclopentadienyl) closes titanium,

Dimethyl two (indenyl) closes zirconium,

Dimethyl indenyl fluorenyl closes zirconium,

The two indenyls of methyl (2-(methylamino) benzyl) close zirconium,

Methyl trimethoxy base silyl two (indenyl) closes zirconium,

Methyl trimethoxy base silyl two (tetrahydro indenyl) closes zirconium,

Methyl-benzyl two (pentamethyl-cyclopentadienyl) closes zirconium,

Dibenzyl two (pentamethyl-cyclopentadienyl) closes zirconium,

Methyl methoxy base two (pentamethyl-cyclopentadienyl) closes zirconium,

Chloromethyl two (pentamethyl-cyclopentadienyl) closes zirconium,

Dimethyl two (methylethyl cyclopentadienyl) closes zirconium,

Dibenzyl two (butyl cyclopentadienyl) closes zirconium,

Dimethyl two (tertiary butyl cyclopentadienyl) closes zirconium,

Dimethyl two (ethyl tetramethyl-ring pentadienyl) closes zirconium,

Dibenzyl two (methyl-propyl cyclopentadienyl) closes zirconium,

Dibenzyl two (trimethyl silyl cyclopentadienyl) closes zirconium,

Dimethylformamide dimethyl base silyl-two (cyclopentadienyls) close zirconium,

Allyl dimethyl base silyl-two (tetramethyl-ring pentadienyl) closes titanium (III),

Dibenzyl dimetylsilyl-two (tertiary butyl cyclopentadienyl) is closed zirconium,

Two (trimethyl silyl) dimetylsilyl-two (n-butyl cyclopentadienyl) are closed zirconium,

2-(dimethylamino) benzyl (methylene-bis (tetramethyl-ring pentadienyl) closes titanium (III),

2-(dimethylamino) benzyl (methylene-bis (n-butyl cyclopentadienyl) closes titanium (III),

Benzyl chloride base dimetylsilyl-two (indenyls) close zirconium,

Dimethylformamide dimethyl base silyl-two (2-methyl indenyl) closes zirconium,

Dimethylformamide dimethyl base silyl-two (2-methyl-4-phenyl indenyl) closes zirconium,

1,4-phenylbenzene-1,3-butadiene dimetylsilyl-two (2-methyl indenyl) closes zirconium,

1,4-phenylbenzene-1,3-butadiene dimetylsilyl-two (2-methyl-4-phenyl indenyl) closes zirconium (II),

1,4-phenylbenzene-1,3-butadiene dimetylsilyl-two (tetrahydro indenyls) close zirconium (II),

Dimethyl two (sec.-propyl amino) borine two bases two (2-methyl-4-phenyl indenyl) close zirconium,

Two (trimethyl silyl) dimetylsilyl-two (tetrahydrofluorenyl) are closed zirconium,

Dibenzyl (isopropylidene) (cyclopentadienyl) (fluorenyl) close zirconium and

Dimethylformamide dimethyl base silyl (tetramethyl-ring pentadienyl) (fluorenyl) closes zirconium.

The another kind of metal complexes of Li Yonging is corresponding to previous structural formula Lp in the present invention ₁MX _mX ' _nX " _p, or its dimer, wherein X is the divalent group of 50 non-hydrogen atoms at the most that forms the metallic ring that has M with Lp.

Preferred divalence X group comprises and contains the group of 30 non-hydrogen atoms at the most, the oxygen that belongs to that comprises the group that is directly connected in delocalization π-bonding, sulphur, at least one atom of the member of boron or the periodic table of elements 14 families, and the nitrogen that is selected from that is connected in M with covalent linkage, phosphorus, in oxygen or the sulphur one homoatomic not.

The preferred 4 family's metal complexes used according to the invention of one class are corresponding to following structural:

Wherein:

M is+2 ,+3, or+titanium or the zirconium of 4 form oxidation state, preferred titanium;

R ³Be selected from hydrogen independently of one another, alkyl, silyl, germyl, cyano group, halogen and their binding substances, this R ³Have 20 non-hydrogen atoms at the most, or adjacent R ³Group forms divalent derivative (that is to say alkylene, silicylene or germanous alkyl) together, thereby forms the condensed ring system,

Each X " be halogen, alkyl,-oxyl or silyl-group, this group has 20 non-hydrogen atoms at the most, and perhaps two X " form neutral C together _5-30Conjugated diolefine or their divalent derivative;

Y is-O--S-,-NR ^*-,-PR ^*-; With

Z is SiR ^* ₂, CR ^* ₂, SiR ^* ₂SiR ^* ₂, CR ^* ₂CR ^* ₂, CR ^*=CR ^*, CR ^* ₂SiR ^* ₂, GeR ^* ₂, or B (NR ^* ₂), R wherein ^*And R ^*Define as the front.

The example of 4 family's metal complexess of a back general formula that can use in enforcement of the present invention comprises:

The trimethylammonium cyclopentadienyl closes titanium,

The trimethylammonium indenyl closes titanium,

Trimethylammonium octahydro amyl group closes titanium,

The trimethylammonium tetrahydro indenyl closes titanium,

The trimethylammonium tetrahydrofluorenyl is closed titanium,

Dimethyl (tertiary butyl amino) (1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydro naphthalene base) dimethylsilane is closed titanium,

Dimethyl (tertiary butyl amino) (1,1,2,3-tetramethyl--2,3,4,9,10-η-1,4,5,6,7,8-hexahydro naphthalene base) dimethylsilane is closed titanium,

Dibenzyl (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium,

Dimethyl (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium,

Dimethyl (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) ethylidene closes titanium,

Dimethyl (tertiary butyl amino) (tetramethyl--η ⁵-indenyl) dimethylsilane is closed titanium,

2-(dimethylamino) benzyl (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (III),

Allyl group (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (III),

2,4-dimethyl pentadiene base (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (III),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (II),

1,3-pentadiene (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (II),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) (2-methyl indenyl) dimethylsilane is closed titanium (II),

2,4-hexadiene (tertiary butyl amino) (2-methyl indenyl) dimethylsilane is closed titanium (II),

2,3-dimethyl-1,3-butadiene (tertiary butyl amino) (2-methyl indenyl) dimethylsilane is closed titanium (IV),

Isoprene (tertiary butyl amino) (2-methyl indenyl) dimethylsilane is closed titanium (IV),

1,3-butadiene (tertiary butyl amino) (2-methyl indenyl) dimethylsilane is closed titanium (IV),

2,3-dimethyl-1,3-butadiene (tertiary butyl amino) (2,3-dimethyl indenyl) dimethylsilane is closed titanium (IV),

Isoprene (tertiary butyl amino) (2,3-dimethyl indenyl) dimethylsilane is closed titanium (IV),

Dimethyl (tertiary butyl amino) (2,3-dimethyl indenyl) dimethylsilane is closed titanium (IV),

Dibenzyl (tertiary butyl amino) (2,3-dimethyl indenyl) dimethylsilane is closed titanium (IV),

1,3-butadiene (tertiary butyl amino) (2,3-dimethyl indenyl) dimethylsilane is closed titanium (IV),

1,3-pentadiene (tertiary butyl amino) (2,3-dimethyl indenyl) dimethylsilane is closed titanium (II),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) (2,3-dimethyl indenyl) dimethylsilane is closed titanium (II),

1,3-pentadiene (tertiary butyl amino) (2-methyl indenyl) dimethylsilane is closed titanium (II),

Dimethyl (tertiary butyl amino) (2-methyl indenyl) dimethylsilane is closed titanium (IV),

Dibenzyl (tertiary butyl amino) (2-methyl indenyl) dimethylsilane is closed titanium (IV),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) (2-methyl-4-phenyl indenyl) dimethylsilane is closed titanium (II),

1,3-pentadiene (tertiary butyl amino) (2-methyl-4-phenyl indenyl) dimethylsilane is closed titanium (II),

2,4-hexadiene (tertiary butyl amino) (2-methyl-4-phenyl indenyl) dimethylsilane is closed titanium (II),

1,3-butadiene (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (IV),

2,3-dimethyl-1,3-butadiene (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (IV),

Isoprene (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (IV),

1,4-dibenzyl-1,3-butadiene (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (II),

2,4-hexadiene (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (II),

The 3-methyl isophthalic acid, 3-pentadiene (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) dimethylsilane is closed titanium (II),

Dimethyl (tertiary butyl amino) (2,4-dimethyl pentadiene-3-yl) dimethylsilane is closed titanium,

Dimethyl (tertiary butyl amino) (6,6-dimethyl cyclohexadienyl) dimethylsilane is closed titanium,

Dimethyl (tertiary butyl amino) (1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydro naphthalene-4-yl) dimethylsilane is closed titanium,

Dimethyl (tertiary butyl amino) (1,1,2,3-tetramethyl--2,3,4,9,10-η-1,4,5,6,7,8-hexahydro naphthalene-4-yl) dimethylsilane is closed titanium,

Dimethyl (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) aminomethyl phenyl silane closes titanium (IV),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) (tetramethyl--η ⁵-cyclopentadienyl) aminomethyl phenyl silane closes titanium (II),

Dimethyl 1-(tertiary butyl amino)-2-(tetramethyl--η ⁵-cyclopentadienyl) ethylidene closes titanium (IV),

1,4-phenylbenzene-1,3-butadiene 1-(tertiary butyl amino)-2-(tetramethyl--η ⁵-cyclopentadienyl) ethylidene closes titanium (II),

2,3-dimethyl-1,3-butadiene (tertiary butyl amino) (3-(N-pyrryl) indenyl) dimethylsilane is closed titanium (IV),

Isoprene (tertiary butyl amino) (3-(N-pyrryl) indenyl) dimethylsilane is closed titanium (IV),

Dimethyl (tertiary butyl amino) (3-(N-pyrryl) indenyl) dimethylsilane is closed titanium (IV),

Dibenzyl (tertiary butyl amino) (3-(N-pyrryl) indenyl) dimethylsilane is closed titanium (IV),

1,3-butadiene (tertiary butyl amino) (3-(N-pyrryl) indenyl) dimethylsilane is closed titanium (IV),

1,3-pentadiene (tertiary butyl amino) (3-(N-pyrryl) indenyl) dimethylsilane is closed titanium (II),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) (3-(N-pyrryl) indenyl) dimethylsilane close titanium (II) and

Dimethyl (tertiary butyl amino) (3-(N-pyrryl) indenes-1-yl) dimethylsilane is closed titanium (IV).

Other catalyzer, the catalyzer that especially contains other 4 family metal is conspicuous for those skilled in the art certainly.Here the metal complexes that preferably uses of topnotch is following metal complexes:

Dimethyl (tertiary butyl amino) dimethyl (tetramethyl-ring pentadienyl) silane closes titanium,

1,3-pentadiene (tertiary butyl amino) dimethyl (tetramethyl-ring pentadienyl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) dimethyl (tetramethyl-ring pentadienyl) silane closes titanium (II),

Dimethyl (cyclohexyl amino) dimethyl (tetramethyl-ring pentadienyl) silane closes titanium,

1,3-pentadiene (cyclohexyl amino) dimethyl (tetramethyl-ring pentadienyl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclohexyl amino) dimethyl (tetramethyl-ring pentadienyl) silane closes titanium (II),

Dimethyl (cyclo-dodecyl amino) dimethyl (tetramethyl-ring pentadienyl) silane closes titanium,

1,3-pentadiene (cyclo-dodecyl amino) dimethyl (tetramethyl-ring pentadienyl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclo-dodecyl amino) dimethyl (tetramethyl-ring pentadienyl) silane closes titanium (II),

Dimethyl (tertiary butyl amino) dimethyl (2-methyl-s-indacen-1-yl) silane closes titanium,

1,3-pentadiene (tertiary butyl amino) dimethyl (2-methyl-s-indacen-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) dimethyl (2-methyl-s-indacen-1-yl) silane closes titanium (II),

Dimethyl (cyclohexyl amino) dimethyl (2-methyl-s-indacen-1-yl) silane closes titanium,,

1,3-pentadiene (cyclohexyl amino) dimethyl (2-methyl-s-indacen-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclohexyl amino) dimethyl (2-methyl-s-indacen-1-yl) silane closes titanium (II),

Dimethyl (cyclo-dodecyl amino) dimethyl (2-methyl-s-indacen-1-yl) silane closes titanium,

1,3-pentadiene (cyclo-dodecyl amino) dimethyl (2-methyl-s-indacen-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclo-dodecyl amino) dimethyl (2-methyl-s-indacen-1-yl) silane closes titanium (II),

Dimethyl (tertiary butyl amino) dimethyl (3,4-(ring penta (1) phenanthrene-1-yl) silane closes titanium,

1,3-pentadiene (tertiary butyl amino) dimethyl (3,4-(ring penta (1) phenanthrene-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) dimethyl (3,4-(ring penta (1) phenanthrene-1-yl) silane closes titanium (II),

Dimethyl (cyclohexyl amino) dimethyl (3,4-(ring penta (1) phenanthrene-1-yl) silane closes titanium,

1,3-pentadiene (cyclohexyl amino) dimethyl (3,4-(ring penta (1) phenanthrene-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclohexyl amino) dimethyl (3,4-(ring penta (1) phenanthrene-1-yl) silane closes titanium (II),

Dimethyl (cyclo-dodecyl amino) dimethyl (3,4-(ring penta (1) phenanthrene-1-yl) silane closes titanium,

1,3-pentadiene (cyclo-dodecyl amino) dimethyl (3,4-(ring penta (1) phenanthrene-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclo-dodecyl amino) dimethyl (3,4-(ring penta (1) phenanthrene-1-yl) silane closes titanium (II),

Dimethyl (tertiary butyl amino) dimethyl (2-methyl-4-phenylindan-1-yl) silane closes titanium,

1,3-pentadiene (tertiary butyl amino) dimethyl (2-methyl-4-phenylindan-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) dimethyl (2-methyl-4-phenylindan-1-yl) silane closes titanium (II),

Dimethyl (cyclohexyl amino) dimethyl (2-methyl-4-phenylindan-1-yl) silane closes titanium,

1,3-pentadiene (cyclohexyl amino) dimethyl (2-methyl-4-phenylindan-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclohexyl amino) dimethyl (2-methyl-4-phenylindan-1-yl) silane closes titanium (II),

Dimethyl (cyclo-dodecyl amino) dimethyl (2-methyl-4-phenylindan-1-yl) silane closes titanium,

1,3-pentadiene (cyclo-dodecyl amino) dimethyl (2-methyl-4-phenylindan-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclo-dodecyl amino) dimethyl (2-methyl-4-phenylindan-1-yl) silane closes titanium (II),

Dimethyl (tertiary butyl amino) dimethyl (3-(1-pyrrolidyl)-indenes-1-yl) silane closes titanium,

1,3-pentadiene (tertiary butyl amino) dimethyl (3-(1-pyrrolidyl)-indenes-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (tertiary butyl amino) dimethyl (3-(1-pyrrolidyl)-indenes-1-yl) silane closes titanium (II),

Dimethyl (cyclohexyl amino) dimethyl (3-(1-pyrrolidyl)-indenes-1-yl) silane closes titanium,

1,3-pentadiene (cyclohexyl amino) dimethyl (3-(1-pyrrolidyl)-indenes-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclohexyl amino) dimethyl (3-(1-pyrrolidyl)-indenes-1-yl) silane closes titanium (II),

Dimethyl (cyclo-dodecyl amino) dimethyl (3-(1-pyrrolidyl)-indenes-1-yl) silane closes titanium,

1,3-pentadiene (cyclo-dodecyl amino) dimethyl (3-(1-pyrrolidyl)-indenes-1-yl) silane closes titanium (II),

1,4-phenylbenzene-1,3-butadiene (cyclo-dodecyl amino) dimethyl (3-(1-pyrrolidyl)-indenes-1-yl) silane closes titanium (II),

Dimethyl 1,2-ethane two (indenes-1-yl) closes zirconium,

1,3-pentadiene 1,2-ethane two (indenes-1-yl) closes zirconium (II),

1,4-phenylbenzene-1,3-butadiene 1,2-ethane two (indenes-1-yl) closes zirconium (II),

Dimethyl 1,2-ethane two (2-methyl-4-phenylindan-1-yl) closes zirconium,

1,3-pentadiene 1,2-ethane two (2-methyl-4-phenylindan-1-yl) closes zirconium (II),

1,4-phenylbenzene-1,3-butadiene 1,2-ethane two (2-methyl-4-phenylindan-1-yl) closes zirconium (II),

Dimethylformamide dimethyl base silane two (indenes-1-yl) closes zirconium,

1,3-pentadiene dimethylsilane two (indenes-1-yl) is closed zirconium (II),

1,4-phenyl-1,3-butadiene dimethylsilane two (indenes-1-yl) is closed zirconium (II),

Dimethylformamide dimethyl base silane two (2-methyl-4-phenylindan-1-yl) closes zirconium (II),

1,3-pentadiene dimethylsilane two (2-methyl-4-phenylindan-1-yl) is closed zirconium (II),

1,4-phenyl-1,3-butadiene dimethylsilane two (2-methyl-4-phenylindan-1-yl) is closed zirconium (II).

Other examples as component 4 family's Metallocenic compounds a) comprise:

Dimethyl two (cyclopentadienyl) closes titanium,

Phenylbenzene two (cyclopentadienyl) closes titanium,

Dimethyl two (cyclopentadienyl) closes zirconium,

Phenylbenzene two (cyclopentadienyl) closes zirconium,

Dimethyl two (cyclopentadienyl) closes hafnium,

Di neo-pentyl two (cyclopentadienyl) closes titanium,

Di neo-pentyl two (cyclopentadienyl) closes zirconium,

Dibenzyl two (cyclopentadienyl) closes titanium,

Dibenzyl two (cyclopentadienyl) closes zirconium,

Chloromethyl two (cyclopentadienyl) closes titanium,

Chloroethyl two (cyclopentadienyl) closes titanium,

Chloro-phenyl-two (cyclopentadienyl) closes titanium,

Chloromethyl two (cyclopentadienyl) closes zirconium,

Chloroethyl two (cyclopentadienyl) closes zirconium,

Chloro-phenyl-two (cyclopentadienyl) closes zirconium,

Brooethyl two (cyclopentadienyl) closes titanium,

The trimethylammonium cyclopentadienyl closes titanium,

The triphenyl cyclopentadienyl closes zirconium,

Three neo-pentyl cyclopentadienyls close zirconium,

The trimethylammonium cyclopentadienyl closes zirconium,

The triphenyl cyclopentadienyl closes hafnium,

Three neo-pentyl cyclopentadienyls close hafnium,

The trimethylammonium cyclopentadienyl closes hafnium,

Trichlorine pentamethyl-cyclopentadienyl closes titanium,

Trichlorine five ethyl cyclopentadienyls close titanium,

Phenylbenzene two (pentamethyl-cyclopentadienyl) closes titanium,

Methylene-bis (cyclopentadienyl) closes titanium;

Dimethyl two (indenyl) closes titanium,

Dichloro two (indenyl) closes titanium,

Dimethyl two (methyl cyclopentadienyl) closes titanium,

Dichloro two (1,2-dimethyl cyclopentadienyl) closes zirconium,

Dimethyl two (1,2-dimethyl cyclopentadienyl) closes zirconium,

Phenylbenzene or dichloro two (1,2-diethyl cyclopentadienyl) close titanium,

Dichloro isopropylidene (cyclopentadienyl) (fluorenyl) closes zirconium,

Dichloro isopropylidene (cyclopentadienyl) (octahydrofluorenyl) closes zirconium,

Dichloro two (4-tolyl) methylene radical (cyclopentadienyl) (fluorenyl) closes zirconium,

Dichloro two (sec.-propyl) methylene radical (cyclopentadienyl) (fluorenyl) closes zirconium,

Dichloro two (4-n-butylphenyl) methylene radical (cyclopentadienyl) (fluorenyl) closes zirconium,

Dichloro two (tertiary butyl) methylene radical (cyclopentadienyl) (fluorenyl) closes zirconium,

Dichloro cyclohexylidene base (cyclopentadienyl) (fluorenyl) closes zirconium,

Dichloro di-isopropyl methylene radical (2,5-dimethyl cyclopentadienyl) (fluorenyl) closes zirconium,

Dichloro isopropylidene (cyclopentadienyl) (fluorenyl) closes hafnium,

Dichloro two (4-tolyl) methylene radical (cyclopentadienyl) (fluorenyl) closes hafnium,

Dichloro di-isopropyl methylene radical (cyclopentadienyl) (fluorenyl) closes hafnium,

Dichloro two (isobutyl-) methylene radical (cyclopentadienyl) (fluorenyl) closes hafnium,

Dichloro di-t-butyl methylene radical (cyclopentadienyl) (fluorenyl) closes hafnium,

Dichloro cyclohexylidene base (cyclopentadienyl) (fluorenyl) closes hafnium,

Dichloro di-isopropyl methylene radical (2,5-dimethyl cyclopentadienyl) (fluorenyl) closes hafnium,

Two chloro isopropyls (cyclopentadienyl) (fluorenyl) close titanium,

Dichloro phenylbenzene methylene radical (cyclopentadienyl) (fluorenyl) closes titanium,

Dichloro di-isopropyl methylene radical (cyclopentadienyl) (fluorenyl) closes titanium,

Dichloro diisobutyl methylene radical (cyclopentadienyl) (fluorenyl) closes titanium,

Dichloro di-t-butyl methylene radical (cyclopentadienyl) (fluorenyl) closes titanium,

Dichloro cyclohexylidene base (cyclopentadienyl) (fluorenyl) closes titanium,

Dichloro ethylenebis (indenyl) is closed zirconium,

Dichloro ethylenebis (4,5,6,7-H-tetrahydroindene-1-yl) is closed zirconium,

Dichloro-dimethyl silicylene two (indenyl) closes zirconium,

Dichloro-dimethyl silicylene two (4,5,6, the 7-H-tetrahydro indenyl) closes zirconium,

Dichloro two (4-tolyl) silylene two (1-indenyl) closes zirconium,

Dichloro two (4-tolyl) silicylene two (4,5,6,7-H-tetrahydrochysene-1-indenyl) closes zirconium,

Dichloro ethidine (1-indenyl) (tetramethyl-ring pentadienyl) closes zirconium,

Dichloro-dimethyl silicylene two (the 2-methyl-4-tertiary butyl-1-cyclopentadienyl) closes zirconium,

Dichloro ethylenebis (1-indenyl) is closed hafnium,

Dichloro ethylenebis (4,5,6,7-H-tetrahydrochysene-1-indenyl) is closed hafnium,

Dichloro-dimethyl silicylene two (indenes-1-yl) closes hafnium,

Dichloro-dimethyl silicylene two (4,5,6,7-H-tetrahydrochysene-1-indenyl) closes hafnium,

Dichloro two (4-tolyl) silicylene two (indenes-1-yl) closes hafnium,

Dichloro two (4-n-butylphenyl) silicylene two (4,5,6,7-tetrahydroindene-1-yl) closes hafnium,

Dichloro ethidine (indenes-1-base-2,3,4,5-tetramethyl--1-cyclopentadienyl) closes hafnium,

Dichloro ethylenebis (indenes-1-yl) is closed titanium,

Dichloro ethylenebis (4,5,6,7-H-tetrahydrochysene-1-indenyl) is closed titanium,

Dimethylformamide dimethyl base silicylene two (2-methyl-4-phenylindan-1-yl) closes zirconium,

Dichloro-dimethyl silicylene two (2-methyl-4-phenylindan-1-yl) close zirconium and

Dichloro ethidine (indenes-1-yl) (2,3,4,5-tetramethyl-ring pentadiene-1-yl) closes zirconium.

Being used for 4 family's metalloceness of the present invention is compound known, or they one of can be by several currently known methodss, such as J.Organomet.Chem., 435,299 (1992) know Organometallics,8,2107 (1989) prepare.A kind of method comprises at first allows the cyclopentadiene of 2 normal optional replacements and metal deprotonation agent react in such as tetrahydrofuran (THF) at organic solvent such as lithium alkylide or potassium hydride KH, and this solution and the 1 normal pair of halogenated compound are such as the solution reaction of dichlorodimethylsilane subsequently.The gained part separates such as distillation or precipitation by usual way then, and with 2 normal metal deprotonation agent reactions, the tetrachloride with 1 normal 4 family's metals reacts then, chooses wantonly with giving body ligand molecular such as tetrahydrofuran (THF) to cooperate in organic solvent once more.

As components b) the solid 4 families metal-magnesium halide complex that is fit to preferably include the halide complex that solid granular contains magnesium and 4 family's metals, especially, solid contains the title complex of magnesium and zirconium or the title complex that solid contains magnesium and hafnium.Except the halogenide structure division, this title complex preferably contains one or more alkoxyl groups and/or aryloxy structure division, especially is selected from oxyethyl group, the structure division in n-butoxy and the ortho-cresol root architecture part.

The halide complex that contains magnesium and 4 family's metals is preferably by the common co-precipitation that is used to prepare the Ziegler-Natta catalyst precursor that contains 4 family's metal halides on the crystallite that is carried on magnesium dihalide known in the art, solid-solid metathesis, or the physical pulverization technology prepares.Preferably, this solid contains the halide complex of magnesium and 4 family's metals by containing magnesium and 4 family's metal construction parts, alkoxyl group and/or aryloxy structure division, the solid granular precursor of halogenide structure division and optional compound of internal electronic donors halogenating agent, especially the halogenide of the 4-13 family metal of the periodic table of elements, especially titanium, the muriate of vanadium and aluminium, most preferably TiCl ₄, VCl ₄, R  AlCl ₂(wherein R  is C _1-12Alkyl, preferred C _1-4Alkyl), their mixture and/or one or more compounds and SiCl ₄The mixture halogenation prepare, obtain the halide complex that solid granular contains magnesium and 4 family's metals.The halide complex that preferred solid granular contains magnesium and 4 family's metals is that wherein the halogenide structure division is those of chloride structure part.

The halide complex (being called precursor here interchangeably) that any solid contains magnesium and 4 family's metals can be used in the present invention, and when preparation catalyst composition of the present invention, any way that becomes known for this type of precursor of halogenation can be used in the halide complex (being called catalyst precursor here interchangeably) that the preparation solid contains magnesium and 4 family's metals.The example of the technology that is fit to is disclosed in US-A 5,034,361; 5,082,907; 5,151,399; 5,229,342; 5,106,806; 5,146,028; 5,066,737; In 5,124,298 and 5,077,357 and other places.

When dialkoxy or two aryloxy magnesium, such as diethoxy magnesium or di-o-cresol magnesium when forming the starting raw material of precursor according to precipitation technology, preferably with magnesium compound and 4 family's metal alkoxide things or halogenated alkoxy 4 family's metal-salts in inert diluent with a spot of 4 family's metal halide, especially TiCl ₄, TiCl ₃, ZrCl ₄, TiCl ₃1/3AlCl ₃Or their mixture merges.The thinner that is fit to comprises aromatic hydrocarbons or halohydrocarbon, perhaps they and one or more pure mixtures.As required, can use a spot of one or more solubilizing agent (being called " shearing agent (clippingagent) "), so that promote the dissolving of one or more metallic compounds.This type of example of shearing agent comprises ortho-cresol, p-cresol, the mixture of ortho-cresol and p-cresol, 3-methoxyphenol, 4-dimethylamino phenol, 2,6 di tert butyl 4 methyl phenol, para-chlorophenol, wintergreen oil, HCHO, CO ₂, B (OEt) ₃, SO ₂, Al (OEt) ₃, Si (OR) ₄, R ' Si (OR) ₃And P (OR) ₃, and following negatively charged ion CO ₃ ^-, Br ^-, (O ₂COEt) ^-The source.In above compound, R and R ' expression alkyl preferably contain the alkyl of 1-10 carbon atom, and preferred R and R ' be identical or different, are methyl or ethyl.The suitable source that above-mentioned negatively charged ion is sheared agent comprises MgBr ₂, carbonization magnesium ethylate (carbonic acid magnesium ethide) and lime carbonate.US-A 5,124,298 and 5,077,357 and other places disclose and sheared the purposes of agent in prepare the precursor title complex that solid granular contains magnesium and 4 family's metals by above-mentioned solid/solid metathesis process.

The preferred diluent of above-mentioned intermediate processing is a halogenated hydrocarbons, especially chlorobenzene or toluene(mono)chloride.Metallic compound, optional shearing agent and thinner merge in digestion step by heating.Preferred temperature is 25-120 ℃, more preferably 30-90 ℃.Use a spot of precipitation agent, preferred aliphatic series alcohol, ethanol especially, propyl carbinol, or their mixture at first promote the dissolving of gained metal complexes.After from mixture, removing alcohol, obtained the precursor title complex that identical shaped solid granular contains magnesium and 4 family's metals with controllable manner.This precursor can wash one or many, uses aliphatic hydrocarbon ideally, and devolatilization as required at last is so that remove volatile contaminant.

Then, contain the precursor title complex halogenation in one or more metathesis steps as previously mentioned of magnesium and 4 family's metals, thereby form the particle and relative low surface area, low porosity magnesium chloride crystallite of the required title complex of solid, relative uniform particle size.The technology of these methods is well-known, for example is disclosed in 5,034,361; 5,082,907; 5,151,399; 5,229,342; 5,106,806; 5,146,028; 5,066,737; 5,077,357; 4,442,276; 4,540,679; 4,547,476; 4,460,701; 4,816,433; 4,829,037; 4,927,797; 4,990,479; 5,066,738; 5,028,671; 5,153,158; 5,247,031; 5,247,032 and elsewhere in.

Be used for precursor conversion is allowed this precursor and halogenating agent here for a kind of appropriate methodology of the solid, particulate state magnesium and the 4 family's metal halide title complexs that use comprises, as titanium tetrachloride, aluminum chloride or alkyl aluminum halide, optional hydrocarbon or halohydrocarbon and optional electron donor(ED) are at liquid diluent, as the existence reaction down of hydrocarbon or halohydrocarbon.Preferred halogenating agent is TiCl ₄Or ethylaluminium dichloride.After chlorination, it is believed that does not have or considerably less residual aluminum alkyls functional group is retained in 4 families metal-magnesium halide complex, so this title complex itself is a non-activity for the polymerization of alkene.

Suitable hydrocarbon or halohydrocarbon preferably contain twelve carbon atom at the most, more preferably 9 carbon atoms at the most.The example of hydrocarbon comprises pentane, octane, benzene, toluene, dimethylbenzene, alkylbenzene or the like.The example of aliphatic halogenated hydrocarbons comprises methylene dichloride, methylene bromide, chloroform, tetracol phenixin, glycol dibromide, vinyl trichloride, trichlorine hexanaphthene, dichlorofluoromethane and tetrachloro octane.The example of aromatic halohydrocarbons comprises chlorobenzene, bromobenzene, dichlorobenzene class and toluene(mono)chloride class.In aliphatic halogenated hydrocarbons, the compound that contains at least two chlorine substituents is preferred, and wherein tetracol phenixin and vinyl trichloride are most preferred.In the middle of aromatic halohydrocarbons, chlorobenzene or toluene(mono)chloride are particularly preferred.

Should optional electron donor(ED) be precursor compound part or the consoluet lewis base compound that does not contain active hydrogen therein.Its use is unusual ideal, so that form tactic polymer, and if desired, is used to form the polymerization of the ethene of narrow molecular weight distributions product.Electron donor(ED) works by being incorporated into some active catalyst position ideally, thereby changes the global reactivity and the limiting catalyst microcrystalline growth of catalyzer, causes products therefrom to have little crystallite dimension and corresponding high surface area.Suitable electron donor(ED) is normally used those compounds in forming the Ziegler-Natta catalyst precursor.Particularly preferred electron donor(ED) comprises ethers, ester class, amine, imines class, nitrile, phosphine class,  class, and Arsiness.Yet preferred electron donor(ED) is aliphatic series and aromatic carboxylic acid's (many) esters or their (many) ether derivants, especially the alkyl ester of aromatic monocarboxylate or dicarboxylic acid and their ether derivant.The example of this type of electron donor(ED) is a methyl benzoate, ethyl benzoate, ethyl p-ethoxybenzoate, the ethyl p-methyl benzoate diethyl phthalate, naphthalene dicarboxylic acids dimethyl esters, o-benzene butyl phthalate ester, terephthalic acid diisopropyl ester and their mixture.Most preferred electron donor(ED) is an ethyl benzoate, and phenylformic acid is to ethoxy ethyl ester and diisobutyl phthalate.

Wherein precursor title complex, optional hydrocarbon or halohydrocarbon, the mode that optional electron donor(ED) contacts with halogenating agent is not crucial.In one embodiment, halogenating agent is joined in the mixture of electron donor(ED) and precursor.Yet more preferably, this electron donor(ED) at first mixes with tetravalent titanium halide and the halohydrocarbon of choosing wantonly, and the gained mixture is used at 70-120 ℃, and preferred 80-115 ℃ high temperature contacts one or many with this precursor title complex down.

The solid product that produces can contact with the halogenated compound of other amount, if desired, contacts with halohydrocarbon in addition.These two operations can in conjunction with, or use separately.In addition, usually usefully also introduce acyl chlorides, for example Benzoyl chloride or phthalyl chloride combine separately or with above-mentioned aftertreatment, are replaced by the halogen structure division with the alkoxyl group structure division in this solid granular magnesium of further promotion and the 4 family's metal halide title complexs.Products therefrom can wash one or many with aliphatic hydrocrbon or hydrocarbon mixture such as octane-iso then, so that remove solubility 4 family's metallicses.

In a preferred embodiment, the mixture of precursor, halogenating agent, optional electron donor(ED) and optional halohydrocarbon at high temperature, for example keeps for some time under 70-150 ℃ temperature in one or more above-mentioned metathesis steps.If material at first contacts under envrionment temperature or about envrionment temperature, heating has obtained optimum so then.Provide enough halogenating agents, so that at least a portion and preferably sizable at least part of the alkoxyl group structure division of this precursor is converted into halogen group.This displacement is carried out in one or more operatings of contacts, and they reach the time that several minutes arrives several hours separately, preferably has halohydrocarbon to exist in each contact process.Enough electron donor(ED)s preferably are provided, make that electron donor(ED) and the mol ratio that is present in the magnesium in magnesium and the 4 family's metal halide title complexs are about 0.01: 1 to about 1: 1, preferably approximately 0.05: 1 to about 0.5: 1.

After forming magnesium and 4 family's metal halide title complexs, it is separated with reaction medium, preferably by filtration, thereby form wet cake.This wet cake washes then ideally, so that remove unreacted halogenating agent, and if desired, can be dry, so that remove residual liquid.In a preferred embodiment, as previously mentioned, extract the filter cake one or many of wet flushing then, so that 4 family's metal contents are reduced to maintenance level.

Extraction comprises allows magnesium and 4 family's metal halide title complexs, and preferred filter cake contact with liquid diluent and with the temperature maintenance of mixture or be elevated to and reach the time that several minutes arrives several hours, separating obtained again solid more than the room temperature.Especially preferably be higher than 45 ℃, preferably be higher than 85 ℃, more preferably be higher than 115 ℃ and most preferably be higher than 120 ℃ to about 300 ℃, more preferably arriving about 200 ℃, contacting this mixture under about 150 ℃ temperature with optimum choosing.

Be preferred for that magnesium of the present invention and 4 family's metal halide title complexs are suitable to have 0.5-15wt%, preferred 0.8-12wt%, the most preferably 4 family's metal contents of 1-10wt%.The weight ratio of 4 family's metals and magnesium suitably is 1: 1-1: 20, preferred 1: 4-1: 15, most preferably about 1: 5-1: 10.

The preferred 4 families metal-magnesium halide complex that here uses is corresponding to formula M g _dTiZr _hAl _i(OR ^e) _eX ^*F (ED) _g, R wherein ^eIndependently be aliphatic series or aromatic hydrocarbyl or COR separately with 1-14 carbon atom ^f, R wherein ^fBe aliphatic series or aromatic hydrocarbyl with 1-14 carbon atom; X ^*Independently be the anion ligand group separately, preferred C _1-4Alkyl, chlorion, bromide anion, or iodide ion, most preferably chlorion; ED is an electron donor(ED); Ti comprises+3 and the cationic mixture of+4 oxidation state, and d is the numerical value of 1-50; E is the numerical value of 0-5; F is the numerical value of 2-100; G is the numerical value of 0-10, and h is the numerical value of 0-2 and the numerical value that i is 0-5.

Can be chosen in the type of the solid 4 family's metal-magnesium complexes that use in the catalyst composition of the present invention, so that required polymer property is provided.In a preferred embodiment, selecting provides broad molecular weight distribution polymers, especially has Alathon and ethene and one or more C of unique high molecular weight block _3-124 family's metal-magnesium complexes of the multipolymer of alkene or diolefine.Determined this type of title complex that here uses contain simultaneously uniquely+3 and+4 oxidation state Ti positively charged ions, Mg ^{+ 2}, Al ^{+ 3}, alkoxyl group and/or aryloxy structure division, the halogen structure division, and seldom or do not have in electron donor(ED).Very preferably this type of 4 family's metal-magnesium complexes are corresponding to following general formula:

Mg ⁺² _5-10Ti ⁺³ _1-2Ti ⁺⁴ _1-2Al ⁺³ _1-10(OR ^e) _1-10X ^* _5-100

R wherein ^eAnd X ^*Define as the front, and preferred each C naturally _1-4Alkyl and chlorine root.They prepare in one embodiment through the following steps: with one or more dialkoxies or two aryloxy magnesium, one or more four titan-alkoxides, the mixture of titanium tetrahalide and three halogenated titaniums (latter is optional to be cooperated with Lewis acid such as aluminum chloride) merges, with the form precipitation of gained title complex with solid particulate, optional use is used to dissolve one or more shearing agent and/or one or more precipitation agents of various components, as alcohols, its the gained solid complexes that removed selective precipitation, at last with this solid particulate halogenation one or many, thereby form MgCl on the spot ₂Crystallite.Preferred halogenating agent is dichloride aluminum alkyls, especially ethylaluminium dichloride.

Though this 4 family metal-magnesium halide complex can be used as solid particulate materials and forms and reclaim, but should be emphasized that, as using in the present invention, this material generally in the forming process of catalyst composition of the present invention by redispersion in organic solvent.Therefore, reclaiming and remove solvent from solid complexes is not crucial for the present invention, can directly use the product by above-mentioned reaction acquisition of slurry or dispersion form on the contrary, need not reclaim in advance and drying.

Any solid particulate materials with other component reaction of this catalyst system and follow-up polyblend can not be used as amount of component b).Suitable material comprises the natural organic or inorganic compound that has or have after treatment low water and surface hydroxyl or other reactive functional mass contg, metal oxide especially, metal nitride, metal carbonate, quasi-metal oxide, organic polymer, silicon polymer and their mixture.Preferably, total hydroxy radical content (comprising physical absorption water and surface hydroxyl functional group) preferably should be less than 0.1mmol/g, is more preferably less than 0.01mmol/g.The example of substrate material comprises: silica, boron nitride, titanium dioxide, zinc oxide, crosslinked polystyrene, glass microspheres, and lime carbonate.Preferably, this filler is also by hydrophobic surface groups or this material other group compatible with hydro carbons characterized.This type of raw material is dispersed in the hydrocarbon diluent that is preferred for the inventive method easily.Hydrophobic silex is preferred, because they are dispersed in the hydrocarbon diluent easily, and has good thixotropic property, thereby gives the gained slurry with high viscosity, and when spraying drying, give the gained spray-dried granules with good intensity.Should have as the solid particulate materials of filler and to be not more than 50 microns, preferably be not more than 10 microns mean particle size.

Suitable filler comprises pyrogenic silica, such as by tetrachloro silicane is added to those that prepare in the oxydizing flame, they by with silane, halogenated silanes, trialkylaluminium, trihydrocarbylborane or similar reagents reaction, thus removed reactive hydroxyl and other surface functional group and given products therefrom with hydrophobicity, and become hydrophobic and to all the other catalyst components, especially the further chemical reaction of 4 family's metal-magnesium complexes is inertia.This type of dewatering filling is called as the passivation filler in this article interchangeably.It is desirable to, this dewatering filling can with organic hydrocarbon liquid, aliphatic series especially, cyclic aliphatic, or aromatic hydrocarbons is miscible, and can in spray-drying process, form the stabilising dispersions of the various components of catalyst composition.Because the surface functional group of passivation, hydrophobic filler, it is compatible with organic liquid, and play thixotropic agent, the viscosity of the dispersion of improved catalysts component in thinner is separated or sedimentation with each component that suppresses to cause product to change, and the improvement drop of giving in the spraying drying operating process forms and the granularity establishment.In addition, this dewatering filling is used for disperseing or the dilute catalyst component, especially solid 4 families metal-magnesium halide complex, so that reduce the local polymerization activity of this catalyzer, thereby prevent the skinning of the local superheating of polymer beads and consequential reactor wall and help feed correct weighing and being assigned in the reactor of uniform catalyst.Appropriate filler has low porosity usually.They preferably have 50 to 500m ²/ g, more preferably 100-400m ²The surface-area of/g, and 0.1 to 10g/ml, preferred 1 to 8g/ml bulk density.

Preferred filler is by fine-grained solids silica or silica precursor are arrived several hours time in 250-600 ℃ of calcining or heating several minutes, with this silica of relief and above-mentioned passivator, especially dichlorodimethylsilane reaction, thus give pyrogenic silica high dry, low hydroxy radical content that products therefrom prepares with hydrophobic performance.Very ideal passivation, dewatering filling are to contain the pyrogenic silica that 0.001 dichlorodimethylsilane that arrives the silane functional of 1.0mmol/g is handled.

Filler with low relatively porosity preferably here uses, this be because metallocene components in the particle hole not by sequester, be retained on the contrary with the approaching particulate surface of solid 4 family's metal-magnesium complexes on, this title complex is a solid, can not enter in the hole of relative porous mass.In fact, the present invention has and contains and the metallocenes of basic inert filler miscellaneous partial concn and the zone of 4 families metal-magnesium halide complex.This has desirably caused the dilution of catalyst activity, thereby has prevented because the excessively local superheating formation of polymerization activity generation.

If desired, use binder component d) so that metallocenes and 4 families metal-magnesium halide component are combined with optional carrier, so that the gained polymerisate is the uniform mixture of polymer product.Because metallocenes is normally lipophilic, and the luxuriant halide complex of 4 family's metal-metals is hydrophilic relatively, be high expectations so this two classes catalyzer is kept appropriate method tight or fully contact in polymerization process.If separate, formed the polymer beads of different performance by these two catalyzer positions, and follow-up processing or transportation can cause the separation of different polymkeric substance.For example, if a kind of catalyst type has formed the small-particle of relative high molecular weight polymers, products therefrom can contain excessive in transportation or course of conveying under action of gravity settled high molecular " particulate ", thereby cause the product heterogeneity.Therefore, the use of binding agent help to prevent component a), b) with optional c) under polymerizing condition, separate.In one embodiment, suitable binding agent contains coordination or the preferred combination functional group in metallocenes and the solid 4 family's metal-magnesium complexes functional group on the two.Scheme can suitably select to have this metallocenes and the title complex that do not need to add binding agent separately and realize the above-mentioned purpose part as an alternative.For example, ionic metal half metallocene or more compatible with 4 families metal-magnesium halide component by becoming the ionic title complex with the activation of the activator of cation is not easy to extract from the mixture that contains two kinds of components.Similarly, contain amine or amino Metallocenic compound energy and components b) magnesium or 4 families' metallicses form Lewis base adducts.Similarly, this binding agent can also have the functional group that is included in the promotor that uses in the final polymerization or its part.Example is the compound with Lewis acid functional or Bronsted acid functional group and non-coordination anion or other activation functional group.

This binding agent can also promote that each component agglomeration of multiphase catalyst composition of the present invention is a particle.Term " heterogeneous " is meant the diacritic zone that keeps the binding substances that contains metallocenes and solid 4 families metal-magnesium halide component after catalyzer forms in the spray-dired catalyst composition of gained.This type of regional filled zone or particle are separated, or are dispersed between the zone or particle of filler.

In one embodiment of the invention, this binding agent is oligomeric or the derivative of polymerization, linearity or ring-type aikyiaiurnirsoxan beta or their trialkylaluminium modification.This compounds can be by containing C ₂Or more tetraalkyl two aikyiaiurnirsoxan beta of senior alkyl are reacted with the trimethyl aluminium that is less than the excessive amount of stoichiometry and are formed.Can also and contain C by methylaluminoxane ₂Or senior alkyl more, especially the reaction of the trialkyl aluminium compound of butyl comes the synthesis modification aikyiaiurnirsoxan beta.As at US-A-5, in 041,584 disclosed like that, contain methyl and more other modified methylaluminoxane of senior alkyl can be by containing C ₂Or the more multi-alkyl aluminium oxygen alkane and the trimethyl aluminium reaction and next synthetic with the water reaction then of senior alkyl.

Aikyiaiurnirsoxan beta is preferred binding agent, because they can also participate in final polymerization as promotor, and only is used for loose or reversibly in conjunction with various catalyst components.As a result, this catalyst composition is division easily in polymerization process, thus make contain component a) and b) the live catalyst position of mixture constantly be exposed to the polymerization environment.The consumption of aikyiaiurnirsoxan beta binding agent that is used to form the agglomerate of required catalyst component generally is less than the necessary amount of activation of the arbitrary catalyst component that is used for olefinic polymerization separately.This spray-dried catalyst composition can also contain the other organic or mineral compound as binding agent, short of disadvantageous effect particle integrity and catalytic activity.This binding agent can also have other function, and final polyolefin product is not oxidized such as stablizing, or improves nascent polymer particulate gas phase fluidization.Other binding agent that is fit to comprises wax, silicon compound, or other material that is fit to.Usually, be benchmark in the weight of solid 4 families metal-magnesium complex component, the molar weight of used binding agent is 1: 1 to 10: 1.

Depend on required final polymer performance, 4 family's metalloceness, 4 families metal-magnesium halide complex and the consumption of filler in composition of the present invention can change significantly.For example, the more substantial if desired lower-molecular-weight component with narrow MWD can use more Metallocenic compound component so.The more substantial if desired high molecular weight component with wideer MWD uses more 4 families metal-magnesium halide complex component so.It is desirable to, the mol ratio of metallocene components and 4 families metal-magnesium halide complex (based on 4 family's metals in each component) is 0.05: 1 to 1: 0.05, preferred 0.1: 1 to 1: 0.1.

Metallocenes, solid 4 families metal-magnesium halide complex and optional binding agent it is believed that with the interface of identical agglomerate at filler or the form of the inclusion between the space and are introduced in the solid heterogeneous catalyst composition that this filler agglomerates is optional by using identical or different binding agent to be incorporated in this agglomerate granule.In addition, if desired, this metallocenes, 4 family's metal-magnesium complexes and/or optional binding agent can covalent linkage or ionic linkage be incorporated into filler particles, but this is optional for operation of the present invention.

When polypropylene, catalyst composition of the present invention can also use selective control agent or SCA.Be adapted at SCA used herein and comprise the silicoorganic compound that contain at least one-oxyl, the ester of monocarboxylic acid or dicarboxylic acid, preferred aromatic monocarboxylate or dicarboxylic acid, and/or their alkyl oxide-or multi-alkyl ether-derivative.The example of the silane compound that is fit to comprises methylcyclohexyl dimethoxy silane (MCHDMS), dimethoxydiphenylsilane (DPDMS), dicyclopentyl dimethoxyl silane (DCPDMS), isobutyl-Trimethoxy silane (IBTMS) and n-propyl Trimethoxy silane (NPTMS).The example of the non-silane SCA that is fit to comprise phenylformic acid to methoxyl group ethyl ester and phenylformic acid to ethoxy ethyl ester.

This catalyst composition passes through to form filler, one or more 4 family Metallocenic compounds and the solid 4 families metal-magnesium halide complex well-beaten suspension in one or more thinners that are fit to, and this suspension of spraying drying prepares then.In a kind of method of this suspension of preparation, solid 4 family's metal halide title complexs are joined in metallocenes and the optional solution or dispersion of binding agent in inert diluent, form first suspension.At least this solid 4 families metal-magnesium halide complex should keep the form of solid particulate and be insoluble to substantially in this diluent mixture.With 1/10 hour to 10 hours time of first suspension stirring, the form with solid or the dispersion in liquid diluent adds filler then.The final suspension of gained is stirred other 1 second to the 3 hours time, and spraying drying then is to remove thinner.Can use identical or different thinner to form various suspension and solution.

Preferably, spraying drying is following carries out: allow this suspension aperture by optionally heating under pressure, there it by optionally heating to the temperature more than the envrionment temperature, preferred 30-100 ℃, subsequently this mixture is sprayed to the inertia dry gas of heating, in the air-flow such as nitrogen, argon gas or propane, with the solid particulate of evaporation thinner and the relative atresia that forms the gained catalyst composition.The preferred obvious volumetric flow rate of the volumetric flow rate of dry gas greater than suspension.In addition, the drop of suspension forms can be by using atomizing nozzle, centrifugal high speed disc atomizer, or known in the art be used for spraying drying relatively other suitable mode of sticking suspension finish.

The thinner that uses in the formation of suspension can dissolve or suspension Metallocenic compound or optional binding agent typically, suspend but do not dissolve 4 families metal-magnesium halide complex and filler, and in spray-drying process evaporable material easily.For example, hydro carbons is such as linearity or branched paraffin hexane for example, pentane and 2-methylbutane; Aromatic substance is such as toluene and dimethylbenzene; With halohydrocarbon such as methylene dichloride, and/or their mixture can effectively be used as thinner.Preferable absorbent has 0-75 ℃ normal boiling point.

The amount that is used to form the filler of suspension is suitably 0.1 to 20, and is preferred 1 to 15, and most preferably 2 to 10wt%, be benchmark in the gross weight of the suspension before the spraying drying.After spraying drying, this filler is with 0.5-50, and the amount of preferred 10-30wt% is present in the gained solid catalyst particle.In addition, it is desirable to, after spraying drying, composition of the present invention exists with particulate form even relatively, atresia, relative low surface area relatively, has the 5-200 micron of for example measuring by laser diffraction grain diameter measurement instrument, 50 hundredths particle diameter D of preferred 10-30 micron by those instruments of Malvern Corporation manufacturing ⁵⁰In addition, this particle preferably has 20 to 300 microns, 90 preferred 15 to 50 microns hundredths particle diameter D90.

The gained catalyst composition can with the protecting materials that is fit to such as mineral oil, so that store and supply with polymerization reactor.In another embodiment, with component a), b), c) and optional d) dispersion in thinner is sprayed in gas-phase olefin polymerization reactor or its collection, the reinforced or recirculation section, in polymerization process, form spray-dired pellet type catalyst composition of the present invention on the spot, thereby do not need catalyst recovery and transfer.

This catalyst composition can be used for ethene and optional higher alkene monomer (preferably having 3-8 carbon atom) and other one or more optional diolefins are aggregated into Alathon and multipolymer.The diene that is fit to especially comprises hexadiene, dicyclopentadiene, divinyl, isoprene, norbornylene, and ethylidene norbornene.

This polymerization process can use equipment well known in the art and operation in gas phase stir or fluidized-bed reactor in, or in sludge phase reactor, carry out.The catalyst composition of vinyl monomer and optional one or more higher alkene monomers and/or one or more diene and significant quantity contacts under the temperature and pressure of initiated polymerization being enough to.This method can be carried out in single reaction vessel or placed in-line two or more reactor.This method is not having catalyzer poison substantially such as moisture, oxygen, and carbonic acid gas carries out under the existence of carbon monoxide and acetylenic compound, just can influence polymerization unfriendly because have been found that only a spot of this type of material.This method can also be carried out in the slurry-phase reactor that uses the thinner that does not dissolve at least some polymeric components.

In polymerization, also use can activated polymerization with the promotor of 4 family's metalloceness and 4 families metal-magnesium complex catalyst component.The example of the promotor that is fit to comprises: (1) comprises the aluminum compound of at least one aluminium-oxygen key, such as contain general formula-(Al (R ) O)-the branching or the cyclic oligomer (oxidation alkyl aluminium) of repeating unit, wherein R  is a hydrogen, contain 1 alkyl to about 12 carbon atoms, the aryl of 6-20 carbon, or the alkaryl of 7-20 carbon, or the halogenated aryl of 6-20 carbon; (2) general formula: [A ⁺] [BAR ^- ₄] ion salt, A wherein ⁺Be positively charged ion Louis or the Bronsted acid that can capture ligand groups from metalloscene catalyst, B is a boron, and A ^RBe the inertia substituted aryl of 6-20 carbon, preferred fluorinated aryl, most preferably perfluorophenyl; (3) Formula B A ^R ₃Boron compound, A wherein ^RAs defined above.

Preferably, this promotor is branching or cyclic oligomer (oxidation alkyl aluminium), also is called aikyiaiurnirsoxan beta.More preferably, this promotor is methylaluminoxane (MAO), also is called methalumoxane, or modified methylaluminoxane (MMAO).

Aikyiaiurnirsoxan beta is well-known in the art, comprises with general formula R  (Al (R ) O) _sThe oligomeric linear alkyl aikyiaiurnirsoxan beta that AlR  represents, and general formula (Al (R ) O) _qThe oligomeric cyclic alkylaluminoxane, wherein s is 1-40, preferred 10-20; Q is 3-40, preferred 3-20; With R  independently be C separately _1-12Alkyl, preferred C _1-4Alkyl, the mixture of most preferable or methyl and butyl.

Being effective to the metalloscene catalyst of catalyst composition and the amount of promotor can change in wide region.When this promotor is linear, branching or cyclic oligomer or polymerization aikyiaiurnirsoxan beta, normally about 2: 1 of the mol ratio of aluminium atom and the atoms metal that contains in this metallocene catalyst compound is to about 10,000: 1, preferably approximately 10: 1 is to about 1,000: 1 and most preferably about 100: 1 to about 700: 1.With component a) and b) amount be benchmark, preferably more preferably 50: 1 to 10,000: 1, most preferably from 200: 1 to 1000: 1 to 100,000: 1 in 5: 1 to the molar weight of whole 4 family's metals for aluminoxane catalyst.Other promotors used to about 10: 1 mol ratio with respect to metallocene components with about 1: 1 usually.

Can introduce common additives in the method, comprise chain-transfer agent, linking agent, static inhibitor helps liquid agent and condensing agent.When hydrogen was used as chain-transfer agent in the method, it used to the amount of about 10mol hydrogen/mol olefinic monomer with about 0.001.Also have,, in this system, can also exist catalyst composition and reagent are any material of inert according to the temperature controlled needs of system.

In polymerization process, can use organometallic compound as scavenging agent, so that remove poisonous substance and increase catalyst activity.Usually, can also be used as scavenging agent with as the identical compound of promotor.The example of useful external catalyst is the metal alkylide class, preferred alkyl aluminium, most preferably triisobutyl aluminium.The use of this type of scavenging agent is well-known in the art.

Polymerization is preferably carried out in fluidized-bed polymerization reactor.According to this method, with catalytically effective amount with the each several part of catalyzer with promotor and institute's continuous or semicontinuous feeding reactor of one or more monomers of the polymeric of being wanted, continuous or semicontinuous discharge polymer product of while.The fluidized-bed reactor that is fit to is disclosed in US-A 4,302,565,4,302,566,4,303,771 and other place in.

Usually preferably, this type of fluidized-bed uses the unreacted monomeric recycle stream operation from fluidized-bed reactor, and its at least a portion condensation is so that remove heat from recycle stream.In addition, can also introduce condensing agent.The condensing mode operation of fluidized-bed reactor is normally known in the art, for example is described in US-A 4,543, in 399 and 4,588,790.Have been found that the use of condensing mode has reduced the amount that dissolves in the dimethylbenzene in the isotactic polyprophlene and improved catalyst performance when using catalyzer of the present invention.

Can use about 0 to about 200 ℃ polymerization temperature and normal atmosphere, sub-atmospheric pressures or superatmospheric pressure.Use the temperature of sub-atmospheric pressures or superatmospheric pressure and 40-100 ℃.Preferably, use 1-1000psi (7kPa is to 7MPa), preferred 50 to 400psi (350kPa is to 2.8MPa), most preferably 100 arrive the pressure of 300psi (700kPa is to 2MPa) and 30-130 ℃, preferably 65-110 ℃ temperature.Stirring or fluidized-bed gas-phase reaction system are useful especially.Usually, common gas fluidized bed method is by containing one or more monomeric materials flows and undertaken by fluidized-bed reactor continuously with the speed that is enough to granular bed is remained under the floating condition under reaction conditions and allowing in the presence of the catalyst composition.From this reactor, discharge the materials flow that contains unreacted monomer continuously, compression, cooling, optional condensation wholly or in part, and be recycled in this reactor.From reactor, discharge product, and the supply monomer is joined in the recycle stream.According to the temperature controlled needs of system, in this air-flow, can also there be catalyst composition and reagent are any gas of inert preferred condensable gas.In addition, as at US-A-4, disclosedly in 994,534 can use and help liquid agent like that, carbon black for example, silica, clay, or talcum.

Polymerization can be carried out in two or more reactors of single reaction vessel or serial or parallel connection.Accurate operation of polymeric and condition roughly are common, but provide the polyolefin product with high relatively bulk density at this olefine polymerizing process that utilizes the polymerizing catalyst that is formed by solid precursor with the amount of the high relatively productivity that reflected this olefin polymerization catalysis.In addition, the polymerisate of producing in the present invention has the fine particle content of attenuating.

Use this spray-dired olefin polymer that contains the catalyst composition production of filler to have excellent form.It is believed that this is because the rare fragmentation before the beginning polymerization of catalyst combination composition granule.Yet when polymerization began, the catalyst combination composition granule resolved into less granules of catalyst easily and continues polymerization with high activity.Therefore, the growth polymerization composition granule is continuing polymerization under the polymerizing condition highly uniformly, is not subjected to changing in quality or decay as the catalyzer that experiences in normal polymerization.This has obtained to have the polymer beads of wide molecular weight distribution and even form., if desired, can use the post-reactor blend or extrude operation more under the situation of the polymer product of high uniformity at needs.

Certainly, the present invention can operate under the situation of clear and definite disclosed any component not not having.The following example is used for further illustrating the present invention, but should not think restrictive.Except as otherwise noted, all parts and percentage are represented by weight.Be meant about 16-18 hour time if the term that uses " spends the night ", if " room temperature " used is meant 20-25 ℃ temperature, and " combination chain alkane " be meant the mixture of hydrogenation propylene oligomer, mainly is C ₆-C ₁₂Isoalkane can IsoparE ^TMTrade mark from Exxon Chemicals, Inc buys.

Embodiment

Use following prescribed term in an embodiment.

Nomenclature

Density (g/ml) is according to the ASTM 1505 based on ASTM D-1928, and the operation C that is used for board product measures.Preparation sheet material is regulated 1 hour down at 100 ℃, to reach the equilibrium crystallization degree, carries out density measurement then in density gradient column.

MMAO is the methylaluminoxane (the 3A type can be buied from AkzoCorporation) of triisobutyl aluminium modification.

MI is melt index (I ₂), press the g/10min report, measure according to ASTM D-1238 (condition E, 190 ℃, 2.1Kg weight).

FI is flow index (I ₂₁), press the g/10min report, measure according to ASTM D-1238 (condition F, 190 ℃, 21Kg weight).

MFR or melt flow rate (MFR) are the ratios of flow index and melt index.It is relevant with the molecular weight distribution of polymkeric substance.

Activity provides with g polymkeric substance/mmolTi/ hour/100psi ethene (690kPa ethene).

The preparation of solid 4 families metal-magnesium halide complex component

By with shown in molar weight following component is merged and the precipitated solid product prepares and contains titanium, magnesium, the precursor composition of halogenide and alkoxyl group structure division: 3.00Mg (OEt) ₂/ 0.10TiCl ₄/ 0.30 (TiCl ₃1/3AlCl ₃)/0.57Ti (OEt) ₄/ 0.20MgBr ₂/ 2.44EtOH/1.02BuOH.

By (0.81g 5.06mmol) joins and containing ethanol (3.4ml), and (0.74g prepares MgBr in 8.19mmol) to the diethyl magnesium alkoxide in the diluent mixture of butanols (2.3ml) and chlorobenzene (1.4ml) with bromine ₂Solution.In the independent vial under nitrogen, with TiCl ₃1/3AlCl ₃(1.52g, 7.6mmol) with the diethyl magnesium alkoxide (8.43g, 73.7mmol) and titanium tetrachloride (0.45g 2.37mmol) mixes in the chlorobenzene of 40ml.When stirring, (95% hexane solution of 3.42g 14.2mmol), adds the chlorobenzene of other 50ml subsequently to add titanium tetraethoxide.This bottle is placed oil bath, reheat to 100 ℃.Add the MgBr of previous preparation fast ₂Mixture is then with this bottle of sealing of lid.

After under 440rpm, stirring 2.5 hours, take off lid, allow the demulcent nitrogen gas stream, reduce till about 10% up to volume by the gained slurry.Under nitrogen atmosphere, filter this warm slurry then.Solid with the chlorobenzene washing once, and is with hexane wash twice, dry under flowing nitrogen again.Reclaimed precursor product (11.7g) with the form of green particles with number average bead diameter of 18 microns.

Precursor slurrying in the hexane of 10ml with about 2.30g.Use about 3 minutes time that ethylaluminium dichloride (EADC, 25% toluene solution of 16ml) is joined in this slurry then.This initial tawny slurry becomes beige.After in being heated to 60 ℃ oil bath, stirring 30 minutes, filter this slurry.Solid with toluene/hexane mixtures (50/50 volume ratio) washing is once used twice of hexane wash and dry under flowing nitrogen then, has obtained the brown powder of 2.23g.

Spray-dired Preparation of catalysts

Embodiment 1

The 4 families metal-magnesium complex component of preparation as mentioned above that adds 5g in the vial in glove box, the 2.3M n-heptane solution of the MMAO (15.6mmol) that is used as binding agent of the hexane of 150ml and 6.8ml.After the gained slurry is stirred about 2 hours, the dichloro of about 1g two (n-butyl cyclopentadienyl) is closed zirconium join in this slurry, again mixture was stirred other 1 hour.Add pyrogenic silica (1.0g, the Cabosil that can buy from CabotCorporation of dichlorodimethylsilane modification ^TMTS-610), the gained mixture is stirred about 30 minutes again.Then this mixture is fed spraying drying instrument (Buchi190 type disk).Reclaimed and contained 2.95%Zr, 6.69%Al, 5.02%Ti, Mg/Ti+Zr ratio are the product (4.0g) of 3.06 dun easy mobility powder type.Reclaim the MMAO of product: the mol ratio of Ti is 2: 1.The D of the spraying drying product that reclaims ⁵⁰Particle diameter is 34 microns.After check, find that this particle is to contain recognizable silica dioxide granule and be dispersed in all the other components in the space between the silica dioxide granule, i.e. the heterogeneous agglomerate of solid of the mixture of 4 families metal-magnesium solid complexes, metallocenes and MMAO.

Embodiment 2:

The 4 families metal-magnesium complex component of preparation as mentioned above that adds 5g in the vial in glove box, the 2.3M n-heptane solution of the hexane of 103.3ml and the MMAO of 34.2ml (78.7mmol).After the gained slurry is stirred about 2 hours, the dichloro of about 1g two (n-butyl cyclopentadienyl) is closed zirconium join in this slurry, the gained mixture is stirred other 1 hour again.Add pyrogenic silica (1.0g, the Cabosil that can buy from CabotCorporation of dichlorodimethylsilane modification ^TMTS-610), the gained mixture is stirred about 30 minutes again.Then this mixture is fed spraying drying instrument (Buchi190 type disk).Reclaimed and contained 3.29%Zr, 7.71%Al, 5.32%Ti, Mg/Ti+Zr ratio are the product (4.0g) of 2.95 dun easy mobility powder type.Reclaim the MMAO of product: the mol ratio of Ti is 2: 1.The D of the spraying drying product that is reclaimed ⁵⁰Particle diameter is 36 microns.This particle is to contain recognizable silica dioxide granule and be dispersed in all the other components in the space between the silica dioxide granule, i.e. the heterogeneous agglomerate of solid of the mixture of 4 families metal-magnesium solid complexes, metallocenes and MMAO.

Embodiment 3:

The 4 families metal-magnesium complex component of preparation as mentioned above that adds 5g in the vial in glove box, and the hexane of 98.5ml and MMAO (the 2.3M n-heptane solution of 6.8ml, 15.6mmol).After the gained slurry is stirred about 2 hours, dichloro two (n-butyl cyclopentadienyl) is closed zirconium (1.0g) join in this slurry, again mixture was stirred other 1 hour.Add pyrogenic silica (0.5g, the Cabosil that can buy from Cabot Corporation of dichlorodimethylsilane modification ^TMTS-610), the gained mixture is stirred about 30 minutes again.Then this mixture is fed spraying drying instrument (Buchi 190 type disks).Reclaimed and contained 2.34%Zr, 14.9%Al, 3.99%Ti, Mg/Ti+Zr ratio are the product (3.5g) of 3.07 dun easy mobility powder type.Reclaim the MMAO of product: the mol ratio of Ti is 10: 1.The D of the spraying drying product that is reclaimed ⁵⁰Particle diameter is 39 microns.This particle is to contain recognizable silica dioxide granule and be dispersed in all the other components in the space between the silica dioxide granule, i.e. the heterogeneous agglomerate of solid of the mixture of 4 families metal-magnesium solid complexes, metallocenes and MMAO.

Embodiment 4

The pre-dry hexane that adds 1000ml in the glass reactor of 5L purging with nitrogen gas adds solid 4 families metal-magnesium halide complex of the 685g of preparation substantially as mentioned above subsequently.Then, add 7% n-heptane solution of the MMAO of 830g, again this reaction mixture was stirred 1 hour.To be dissolved in dichloro two (n-butyl cyclopentadienyl) in the 1000ml toluene and close zirconium (136g) and join in the reactor, again mixture be stirred other 1 hour.Add pyrogenic silica (780g, the Cabosil that can buy from Cabot Corporation of dichlorodimethylsilane modification ^TMTS-610), the gained mixture is stirred about 30 minutes again.Use rotary atomizer with this mixture spraying drying then.Output is 1.1 kilograms solid.Analyze (%): Zr:2.57, Si:19.4, Al:4.77, Ti:3.02 and Mg/Ti+Zr ratio are 2.95.Reclaim the MMAO of product: the mol ratio of Ti is 2: 1.The D of the spraying drying product that is reclaimed ⁵⁰Particle diameter is 34 microns.This particle is to contain recognizable silica dioxide granule and be dispersed in all the other components in the space between the silica dioxide granule, i.e. the heterogeneous agglomerate of solid of the mixture of 4 families metal-magnesium solid complexes, metallocenes and MMAO.Fig. 1 has enclosed the scanning-tunnelling electron photomicrograph of products therefrom.The form of gained spray-dried catalyst composition looks like heterogeneous agglomerate, and wherein silica dioxide granule (white) presents 4 dark-coloured family's metal-magnesium complex/metalloceness and regional loose combination of MMAO with heavy atom amount atom owing to higher concentration.

Slurry polymerization

In 1L stirred autoclave reactor, add the 485ml hexane, the 15ml1-hexene, the MMAO promotor and obtain about 1 μ mol[Ti+Zr] the capacity catalyzer (form of the slurry in mineral oil) of carrying capacity.Under the pressure reduction of 25psi (170kPa), add hydrogen (700ml), temperature is increased to 70 ℃ again.Feeding ethene to keep required reactor pressure, is controlled at the temperature in the polymerization process below 85 ℃.After 30 minutes, stop the ethene feeding, granular polyethylene is reclaimed in cooling reactor and emptying.The result provides in table 1.

Table 1

Test	Catalyzer	Temperature (℃)	MMAO∶Ti ^*	Active	FI	MFR
Test	Catalyzer	Temperature (℃)	MMAO∶Ti ^*	Active	FI	MFR	1	Embodiment 1	100	1000	79,843	387	146
2	Embodiment 2	120	“	60,098	151	82	1	Embodiment 1	100	1000	79,843	387	146
2	Embodiment 2	120	“	60,098	151	82	3	Embodiment 3	120	“	71,848	-	-
4	Embodiment 4	120	“	53,256	170	106	3	Embodiment 3	120	“	71,848	-	-

The mol ratio of the MMAO promotor that is * added

Vapour phase polymerization

Evaluate root is according to the spray-dried catalyst of embodiment 4 preparations in gas fluidized bed reactor.By it is contacted in n-heptane solution with the MMAO promotor, so that required Al to be provided: the Ti mole recently activates this catalyzer in advance before being incorporated into reactor.Add enough hydrogen, so that 0.007 (H to be provided ₂/ C ₂H ₄) mol ratio.Provide enough 1-hexenes, to obtain 0.011 (C ₆H ₁₂/ C ₂H ₄) mol ratio.The partial condensation reactor content of recirculation is used for the controlling reactor temperature.The result provides in table 2.

Table 2

Test	C ₂H ₄ (MPa)	Temperature (℃)	MMAO∶Ti ^*	Active	FI	MI	Density	Ti ^** (ppm)
Test	C ₂H ₄ (MPa)	Temperature (℃)	MMAO∶Ti ^*	Active	FI	MI	Density	Ti ^** (ppm)	5	1.0	94	1812	79,843	7.63	0.22	0.948	0.39
6	1.4	80	1590	60,098	6.21	0.11	0.943	0.36	5	1.0	94	1812	79,843	7.63	0.22	0.948	0.39
6	1.4	80	1590	60,098	6.21	0.11	0.943	0.36	7	1.4	105	1048	71,848	8.93	0.35	0.949	0.36

The mol ratio of the MMAO promotor that is * added

The residual Ti of * in polymkeric substance

Claims

But 1, combine with promotor and be used for the heterogeneous spray-dired catalyst composition of the monomeric polymeric solid granular of addition polymerization, comprising:

A) 4 family's Metallocenic compounds;

B) contain magnesium at least, the solid 4 families metal-magnesium halide complex of 4 group 4 transition metals and halid structure division;

C) the particulate inert filler and

D) binding agent, it can with component a) and b) and optional c) be combined into the heterogeneous agglomerate of particulate state, and do not have its catalytic performance of disadvantageous effect.
2, as the desired catalyst composition of claim 1, wherein 4 families metal-magnesium halide complex contain simultaneously+3 and+4 oxidation state Ti positively charged ions, Mg ^{+ 2}, Al ^{+ 3}, alkoxyl group and/or aryloxy structure division, the halogen structure division, and seldom or do not have in electron donor(ED).
3, as the desired catalyst composition of claim 2, wherein 4 family's metallized metals are luxuriant is zirconocene.
4, as the desired catalyst composition of claim 1, wherein metallocenes is that dichloro two (n-butyl cyclopentadienyl) closes zirconium.
5, as the desired catalyst composition of claim 1, wherein binding agent is an aikyiaiurnirsoxan beta.
6, as the desired catalyst composition of claim 5, wherein binding agent is a methylaluminoxane.
7, but preparation combines the method that is used for the heterogeneous spray-dired catalyst composition of the monomeric polymeric solid granular of addition polymerization with promotor, comprises forming the mixture that contains following component:

A) 4 family's Metallocenic compounds;

B) contain magnesium at least, the solid 4 families metal-magnesium halide complex of 4 group 4 transition metals and halid structure division;

C) particulate inert filler; With

D) binding agent, it can with component a) and b) and/or c) be combined into the heterogeneous agglomerate of particulate state, and do not have its catalytic performance of disadvantageous effect; With

E) organic volatile liquid diluent;

And with this mixture spraying drying, so that remove thinner and the product that stays solid particulate form.