CN100484969C - Polymerization method - Google Patents

Abstract

The present invention provides catalyst compositions useful in polymerization processes, including a Group 15 containing metal compound, mixed catalyst compositions including the Group 15 containing metal compound and a second metal compound which is preferably a bulky ligand metallocene catalyst, supported and unsupported catalyst systems thereof, and a process for polymerizing olefin utilizing them. The invention also discloses a new polyolefin, generally polyethylene, particularly a multimodal polymer and more specifically, a bimodal polymer, and its use in various end-use applications such as film, molding and pipe.

Description

Polymerization process

Invention field

The present invention relates to comprise the catalyst composition of the metallic compound that contains the 15th family's element and comprise the mixed catalyst composition of at least two kinds of metallic compounds.At least a metallic compound of preferred described mixed catalyst composition is the metallic compound that contains the 15th family's element.More preferably described another kind of metallic compound is big ligand metal cyclopentadienyl catalyst compound.The invention still further relates to the catalyst system that uses described catalyst composition, and the application in olefinic polymerization.The invention still further relates to a kind of new polyolefine, be generally polyethylene, particularly multi-modal polymer more specifically is a bimodal polymers, and in such as film, moulded product and pipe various uses is arranged.

Background of invention

The progress of polymerization and katalysis can have been produced many novel polymers that the physics that is applicable to various excellent product and application and chemical property are improved.Along with the exploitation of raw catalyst, the selection that is used to produce the polymeric type (solution, slurry, high pressure or gas phase) of particular polymers enlarges.And the progress of polymerization technique has formed improving one's methods that efficient is higher, productive rate is higher and economic.These progressive examples are development of big ligand metal ocene catalyst system utilisation technology.

Recently found multiple tooth heteroatoms anion ligand, as described in following document: (1) Kempeet al., " Aminopyridinato Ligands-New Directions andLimitations ", 80th Canadian Society for Chemistry Meeting, Windsor, Ontario, Canada, June 1-4,1997; (2) Kempe et al., Inorg.Chem.1996 vol 35 6742; (3) Jordan et al. is based on polyolefin catalyst (Bei, the X. of hydroxyquinoline; Swenson, D.C.; Jordan, R.F., Organometallics 1997,16, and 3282); (4) Horton, et al., " CationicAlkylzirconium Complexes Based on a Tridentate Diamide Ligand:New Alkene Polymerization Catalysts ", Organometallics, 1996,15,2672-2674 relates to three tooth zirconium complexs; (5) Baumann, et al., " Synthesisof Titanium and Zirconium Complexes that Contain the TridentateDiamido Ligand[((t-Bu-d ₆) N-O-C ₆H ₄) ₂O] ^2-{ [NON] } ^2-) and the LivingPolymerization of 1-Hexene by Activated[NON] ZrMe2 ", Journalof the American Chemical Society, Vol.119, pp.3830-3831; (6) Cloke et al., " Zirconium Complexes incorporating the NewTridentate Diamide Ligand[(Me ₃Si) N{CH ₂CH ₂N (SiMe ₃) ₂] ^2-(L); TheCrystal Structure of[Zr (BH ₄) ₂L] and[ZrCl{CH (SiMe ₃) ₂L] ", J.Chem.Soc.Dalton Trans, pp.25-30,1995; (7) Clark et al., " Titanium (IV) complexes incorporating the aminodiamide ligand[(SiMe ₃) N{CH ₂CH ₂N (SiMe ₃) ₂] ^2-(L); The X-ray crystal structure of[TiMe ₂(L)] and[TiCl{CH (SiMe ₃) ₂(L)] ", Journal ofOrganometallic Chemistry, Vol 50, pp.333-340,1995; (8) Scollardet al., " Living Polymerization of alpha-olefins by ChelatingDiamide Complexes of Titanium ", J.Am.Chem.Soc., Vol 118, No.41, pp.10008-10009,1996; (9) Guerin et al., " Conformationally Rigid Diamide Complexes:Synthesis andStructure of Titanium (IV) Alkyl Derivatives ", Organometallics, Vol 15, No.24, pp.5085-5089,1996.

In addition, EP 0 874 005A1 disclose a kind of polymerizing catalyst that includes the substituent phenates compound of imines.WO98/37106 discloses a kind of transition metal complex that contains the heterocyclic fused cyclopentadiene part of the 13rd, 15 or 16 families.WO99/01460 discloses the catalyst precursor compound, comprise contain heterocycle and with the heteroatomic part of described loop section bonding.WO99/46303 and WO99/46304 disclose the metal complexes that the substituent pyridyl ligands of imines is arranged.

In addition, US 5 576 460 describes a kind of preparation of arylamines part, US 5 889 128 discloses a kind of alkene living polymerisation process, and using has an atoms metal and two the 15th family's atoms to be arranged and the initiator of the part of one the 16th family's atom or three the 15th family's atoms.EP 893 454A1 have also described the transition metal aminocompound that is preferably titanium.In addition, US 5 318 935 has discussed amino transistion metal compound and has been specially adapted to produce the catalyst system of isotactic polyprophlene.Also discussed the polymerizing catalyst that contains bidentate and tridentate ligand among the US 5 506 184.

The polymkeric substance that traditional big ligand metal ocene catalyst system produces is difficult to be processed into film in some cases, for example uses old extrusion moulding apparatus.One of technology of improving these polymkeric substance is to make it to have the blend that requires character that each component has separately with other polymkeric substance blending with generation.Though the easier processing of these blend polymers is very expensive, and described production/manufacturing process has increased the blend step of trouble.

Higher molecular weight makes polymkeric substance have the ideal mechanical property, forms stable bubble in producing film.But this performance also hinders extrusion molding processing because of increasing forcing machine internal return pressure, impels to produce the melt fracture defective in the inflation bubble, and causes the orientation degree of final film too high potentially.The catalyst system that contains multiple tooth heteroatoms anion ligand is tending towards producing the polymkeric substance of ultra high molecular weight.For remedying this defective, can allocate second component of a small amount of lower molecular weight polymkeric substance into and return pressure and suppress melt fracture to reduce forcing machine.Some commercial runs are produced high density polyethylene(HDPE) (HDPE) product of machinable bimodal molecular weight distribution (MWD) with the multiple reactor technological operation based on this principle.HIZEX ^TM, Mitsui Chemicals HDPE product is the world standard of generally acknowledging.HIZEX ^TMTwo or multiple reactor method with costliness is produced.In the multiple reactor method, each reactor produces a kind of component of described finished product.

This area also attempts to produce two kinds of polymkeric substance simultaneously with two kinds of different catalysts in same reactor.WO99/03899 is disclosed in and uses typical big ligand metal cyclopentadienyl catalyst and traditional Ziegler-Natta catalyst to produce bimodal polyolefin in the same reactor.But using two kinds of dissimilar catalyzer to produce its feature can not be by the polymkeric substance of the polymkeric substance of every kind of Catalyst Production of independent use prediction.Because of the competition between catalyst system therefor or the catalyst system or other influence this Unpredictability appears for example.

The polyethylene that density is higher and molecular weight is higher is valuable in requiring the high film application of rigidity height, good toughness and output.This polymkeric substance is also very important in the pipe applications that requires rigidity, toughness and weather resistance, particularly resisting environmental stress and cracking.

Therefore, need improved catalyst compound and can produce the catalyst combination of the polyethylene polymer processed that (preferably in single reaction vessel) has the desirable combination of processing, machinery and optical property.

Summary of the invention

The invention provides catalyst compound, catalyst system and hybrid catalyst system, and the application in polymerization process, by the polymkeric substance of its production and the product made by described polymkeric substance.

In one embodiment, the present invention relates to a kind of catalyst compound that comprises the metallic compound that contains the 15th family's element, with the mixed catalyst composition that comprises at least two kinds of metallic compounds, at least a metallic compound of wherein said mixed catalyst composition is the metallic compound that contains the 15th family's element, and another kind of metallic compound is big ligand metal cyclopentadinyl compound, traditional transition-metal catalyst or its combination; The catalyst system that comprises these catalyzer; Their application and polymkeric substance prepared therefrom in olefinic polymerization.

In another embodiment, the present invention relates to contain the 3rd to 14 family's metallic compound of two or three-fold coordination of the 15th family's element, preferred the 3rd to 7 family, more preferably the 4th to 6 family even more preferably group-4 metal catalyst compound, with the mixed catalyst composition that comprises at least two kinds of metallic compounds, wherein at least a metallic compound is the above-mentioned catalyst compound that contains the 15th family's element, and another kind of metallic compound is big ligand metal cyclopentadinyl compound, traditional transition-metal catalyst or its combination; The catalyst system that comprises these catalyzer; Their application and polymkeric substance prepared therefrom in olefinic polymerization.In this embodiment, preferred described another kind of metallic compound is big ligand metal cyclopentadinyl compound.

In another embodiment, the present invention relates to the 3rd to 14 family's atoms metal and at least one leavings group bonding and with at least two the 15th family's atomic linkages, described the 15th family's atom is the catalyst compound by another group and the 15th or 16 family's atomic linkages one of at least also, with the mixed catalyst composition that comprises at least two kinds of metallic compounds, wherein a kind of metallic compound is the above-mentioned catalyst compound that contains the 15th family's element, second kind of metallic compound is different with first kind of metallic compound, is big ligand metal cyclopentadienyl catalyst, traditional transition-metal catalyst or its combination; The catalyst system that comprises these catalyzer; Their application and polymkeric substance prepared therefrom in olefinic polymerization.

In another embodiment, the present invention relates to the carrying method of catalyst composition described herein; Load type catalyst system; With they application in olefinic polymerization.

In another embodiment, the present invention relates to contain the application of aluminium Lewis acid activation agent in described catalyst composition and catalyst system.

In another embodiment, the present invention relates to described catalyst composition and catalyst body and tie up to the method that infeeds polymerization reactor in the carrier fluid.

In another embodiment, the present invention relates to method, particularly with gas phase or slurry phase method with arbitrary catalyst system described herein or load type catalyst system olefin polymerization.

In another embodiment, the present invention relates to method, particularly in single polymerization reactor with mixed catalyst composition olefin polymerization described herein.More preferably described method utilizes successive gas phase single reactor method to produce multi-modal polymer.

In another embodiment, the present invention relates to polymkeric substance, preferred new bimodal MWD HDPE with above-mentioned mixed catalyst composition preparation.

The accompanying drawing summary

Fig. 1 is the diagram of back example 1.

Fig. 2 is the diagram of back example 2.

Fig. 3 is the diagram of back example 3.

Fig. 4 is the diagram of back example 4.

Fig. 5 shows down 5 diagram for the back.

Fig. 6 is the diagram of back example 6.

Fig. 7 is the diagram of back example 7.

Fig. 8 is the diagram of back example 8.

Fig. 9 is the diagram of back example 9.

Detailed Description Of The Invention

Preface

The present invention relates to contain the application of metal catalyst compounds in olefinic polymerization of the 15th family's element. In addition, the applicant finds that catalyst compounds and another kind of catalyst (preferred large ligand metal cyclopentadinyl compound) that these contain the 15th family's element are used in combination the new bimodal MWD HDPE product of generation. Unexpectedly, mixed catalyst composition of the present invention can use in the single reactor system.

The metallic compound that contains the 15th family's element

The described compound that contains the 15th family's element generally comprise with at least one leaving group bonding and with the 3rd to 14 family's metallic atom of at least two the 15th family's atomistic bindings, preferred the 3rd to 7 family, more preferably the 4th to 6 family even more preferably group-4 metal atom, described the 15th family's atom is one of at least also by another group and one the 15th or 16 family's atomistic bindings.

In one embodiment, described the 15th family's atom is one of at least also by being selected from C₁To C₂₀Alkyl, another group that contains heteroatomic group, silicon, germanium, tin, lead or phosphorus and one the 15th or 16 family's atomistic bindings, the wherein said the 15th or 16 family's atoms can be not with other group bonding or also with hydrogen, the group that contains the 14th family's atom, halogen or contain heteroatomic group bonding, one of described two the 15th family's atoms are also with a cyclic group bonding and alternatively with hydrogen, halogen, hetero atom or alkyl or contain heteroatomic group bonding.

In another embodiment, the present invention contains the metallic compound of the 15th family's element can be by representing with following formula I or formula II:

Formula I or

Formula II

Wherein M is the 3rd to 12 group 4 transition metal or the 13rd or 14 main group metals, preferred the 4th, 5 or 6 family's metals, and more preferably group-4 metal, most preferably zirconium, titanium or hafnium,

Each X is leavings group independently, the preferred anionic leavings group, and more preferably hydrogen, alkyl, heteroatoms or halogen, alkyl most preferably,

Y is 0 or 1 (y is 0 o'clock, does not have L),

N is the oxidation state of M, preferred+3 ,+4 or+5, more preferably+4,

M is the formal charge of described YZL or YZL ' part, and is preferred 0 ,-1 ,-2 or-3, more preferably-2,

L is the 15th or 16 family's elements, preferred nitrogen,

L ' is the 15th or 16 family's elements or the group that contains the 14th family's element, preferred carbon, silicon or germanium,

Y is the 15th family's element, preferred nitrogen or phosphorus, and more preferably nitrogen,

Z is the 15th family's element, preferred nitrogen or phosphorus, and more preferably nitrogen,

R ¹And R ²Be C independently ₁To C ₂₀Alkyl, containing of maximum 20 carbon atoms of heteroatomic group, silicon, germanium, tin, lead or phosphorus are arranged, preferred C ₂To C ₂₀Alkyl, aryl or aralkyl, more preferably line style, branching or cyclic C ₂To C ₂₀Alkyl, most preferably C ₂To C ₆Alkyl,

R ³Do not exist or be alkyl, hydrogen, halogen or contain heteroatomic group, preferably have line style, ring-type or the branched-alkyl of 1 to 20 carbon atom, more preferably R ³Do not exist or for hydrogen or alkyl, most preferably be hydrogen,

R ⁴And R ⁵Be cycloalkyl, the ring-type aralkyl of aryl, cycloalkyl, the replacement of alkyl, aryl, replacement, the ring-type aralkyl or the polycyclic system of replacement independently, preferably have maximum 20 carbon atoms, 3 to 10 carbon atoms are more preferably arranged, even more preferably C ₁To C ₂₀Alkyl, C ₁To C ₂₀Aryl or C ₁To C ₂₀Aralkyl or contain heteroatomic group such as PR ₃, wherein R is an alkyl,

R ¹And R ²Can interconnect each other, and/or R ⁴And R ⁵Can interconnect each other,

R ⁶And R ⁷Do not exist independently or be hydrogen, alkyl, halogen, heteroatoms or alkyl, preferably have line style, ring-type or the branched-alkyl of 1 to 20 carbon atom, more preferably do not exist and

R* do not exist or for hydrogen, the group that contains the 14th family's atom, halogen, contain heteroatomic group.

" described YZL or YZL, the formal charge of part " means the electric charge of the whole part that does not have described metal and described leavings group X.

" R ¹And R ²Also can interconnect " mean R ¹And R ²Can directly interconnect, also can interconnect by other group." R ⁴And R ⁵Also can interconnect " mean R ⁴And R ⁵Can directly interconnect, also can interconnect by other group.

Alkyl can be line style, branched-alkyl or alkenyl, alkynyl, cycloalkyl or aryl, fatty acyl group, aroyl, alkoxyl group, aryloxy, alkylthio, dialkylamino, carbalkoxy, aryloxy carbonyl, formamyl, alkyl-or dialkyl-7-amino formyl radical, acyloxy, amido, aromatic acylamino, straight chain, side chain or cyclic alkylidene or its combination.Aralkyl is defined as the aryl of replacement.

In one preferred embodiment, R ⁴And R ⁵Be group shown in the following formula independently:

Formula 1

R wherein ⁸To R ¹²Be hydrogen, C independently ₁To C ₄₀Alkyl, halogen, heteroatoms, contain containing of 40 carbon atoms of heteroatomic group, preferred C at most ₁To C ₂₀Line style or branched-alkyl, preferable methyl, ethyl, propyl group or butyl, any two R bases can form cyclic group and/or heterocyclic group.Described cyclic group can be an aromatics.In one preferred embodiment, R ⁹, R ¹⁰And R ¹²Be methyl, ethyl, propyl group or butyl (comprising all isomer) independently, in the preferred embodiment, R ⁹, R ¹⁰And R ¹²Be methyl, R ⁸And R ¹¹Be hydrogen.

In one particularly preferred embodiment, R ⁴And R ⁵Be group shown in the following formula:

Formula 2

In this embodiment, M is a group-4 metal, preferred zirconium, titanium or hafnium, even more preferably zirconium; L, Y and Z are nitrogen; R ¹And R ²Be CH ₂-CH ₂-; R ³Be hydrogen; R ⁶And R ⁷Do not exist.

In one preferred embodiment, the alkyl of at least one X for replacing preferably has the substituted alkyl more than 6 carbon atoms, most preferably the alkyl of aryl replacement.Most preferably the alkyl of aryl replacement is a benzyl.

In one particularly preferred embodiment, the described metallic compound that contains the 15th family's element is expressed from the next:

Compound I

In the Compound I, Ph equals phenyl.

The metallic compound that contains the 15th family's element of the present invention prepares by methods known in the art, as drawing disclosed method in the reference among EP 0 893 454A1, US 5 889 128 and the US 5 889 128, all is incorporated herein for reference.The USSN 09/,312 878 of application on May 17th, 1999 discloses the gas phase or the slurry phase polymerisation method of the two ammonia catalyzer of working load type, also is incorporated herein for reference.

The preferred direct synthesis technique of these compounds comprises: make described neutral ligand (seeing YZL or the YZL of formula I for example or II) and M ⁿX _n(M is the 3rd to 14 family's metal, n is the oxidation state of M, each X is anion-radicals such as halogen ion) be higher than in other solvent of 60 ℃ in about 20 to about 150 ℃ (preferred 20 to 100 ℃) reaction 24 hours or longer time down at non-coordination or weak ligand solvent such as ether, toluene, dimethylbenzene, benzene, methylene dichloride and/or hexane or boiling point, use then excessive (as 4 or more equivalents) alkylating agent handle in ether as methylmagnesium-bromide as described in mixture.Remove by filter described magnesium salts, separate described metal complexes by standard technique.

In one embodiment, the described metallic compound that contains the 15th family's element prepares by the following method: make neutral ligand (seeing the YZL or the YZL ' of formula 1 for example or 2) and M ⁿX _n(M is the 3rd to 14 family's metal, n is the oxidation state of M, each X is the negatively charged ion leavings group) in non-coordination or weak ligand solvent in about 20 ℃ or higher (preferred about 20 to about 100 ℃) reaction down, handle described mixture with excessive alkylating agent then, reclaim described metal complexes.In one preferred embodiment, the boiling point of described solvent is higher than 60 ℃, as toluene, dimethylbenzene, benzene and/or hexane.In another preferred embodiment, described solvent comprises ether and/or methylene dichloride, the two arbitrary all preferred.

Big ligand metal cyclopentadinyl compound

In one embodiment, the above-mentioned metallic compound that contains the 15th family's element can be combined to form mixed catalyst composition with second kind of metallic compound.Described second kind of metallic compound is preferably big ligand metal cyclopentadinyl compound.

Usually, big ligand metal cyclopentadinyl compound includes the full sandwich compound of half-sum of the bulky ligand of one or more and at least one atoms metal bonding.Typical big ligand metal cyclopentadinyl compound is generally described as one or more bulky ligand and one or more leavings group that comprises with at least one atoms metal bonding.In one preferred embodiment, at least one bulky ligand and described atoms metal η-bonding are most preferably with described atoms metal η ⁵-bonding.

Described bulky ligand generally is combined as representative with one or more open type, acyclic or condensed ring or ring system or its.These bulky ligand (preferred described ring or ring system) typically are made up of the atom that is selected from the periodic table of elements the 13rd to 16 family's atom, and preferred described atom is selected from carbon, nitrogen, oxygen, silicon, sulphur, phosphorus, germanium, boron and aluminium or its combination.Most preferably described ring or ring system are made up of carbon atom, for example (but being not limited to) those cyclopentadienyl ligands or cyclopentadienyl-type ligands structure or other similar functions ligand structure such as pentadiene, inferior cyclooctatetraene base or imido (imide) part.Described atoms metal is preferably selected from the periodic table of elements the 3rd to 15 family and lanthanum or actinium series.Preferred described metal is the transition metal of the 4th to 12 family, the more preferably transition metal of the 4th, 5 and 6 families, and most preferably described transition metal is from the 4th family.

In one embodiment, described big ligand metal cyclopentadienyl catalyst compound is expressed from the next:

L ^AL ^BMQ _n (III)

Wherein M is the atoms metal of the periodic table of elements, can be the periodic table of elements the 3rd to 12 family's metal or lanthanum or actinide elements, and preferred M is the 4th, 5 or 6 group 4 transition metals, and more preferably M is the 4th group 4 transition metal, even more preferably M is zirconium, hafnium or titanium.Described bulky ligand L ^AAnd L ^BBe open type, acyclic or condensed ring or ring system and any assistant ligand system, comprise that the cyclopentadienyl ligands that do not replace or replace or cyclopentadienyl-type ligands, heteroatoms replace and/or contain heteroatomic cyclopentadienyl-type ligands.The non-limitative example of bulky ligand comprises cyclopentadienyl ligands, cyclopenta phenanthryl part, indenyl ligands, benzindene ylidene ligands, fluorenyl ligand, octahydrofluorenyl part, inferior cyclooctatetraene ylidene ligands, cyclopenta cyclododecene part, nitrence ylidene ligands, azulene part, pentalene part, phosphoryl (phosphoy1) part, phosphinimine (WO99/40125), pyrryl part, pyrazolyl part, carbazyl part, the assorted benzene part of boron etc.; comprise its hydrogenation variant, for example the tetrahydro indenyl part.In one embodiment, L ^AAnd L ^BCan be can with M η-bonding, preferably with M η ³-bonding, η most preferably ⁵Any other ligand structure of-bonding.In another embodiment, L ^AOr L ^BAtom and molecule amount (MW) surpass 60a.m.u., be preferably greater than 65a.m.u..In another embodiment, L ^AAnd L ^BCan comprise one or more heteroatoms for example nitrogen, silicon, boron, germanium, sulphur and phosphorus, be combined to form open type, acyclic or preferred condensed ring, ring or ring system with carbon atom, for example heterocyclic pentylene Kiev helps part.Other L ^AAnd L ^BBulky ligand includes but not limited to huge amino, phosphide, pure root, phenol root, imino-, carbolides, borollides, porphyrin, phthalocyanine, corrin and the big ring of other polyazo.Each L ^AAnd L ^BCan be identical or different type and the bulky ligand M bonding independently.In one embodiment of formula (III), only there is L ^AOr L ^BOne of.

Independently, each L ^AAnd L ^BThe combination of can be unsubstituted or being substituted basic R replaces.The non-limitative example of substituent R comprise the alkyl, alkenyl, alkynyl, cycloalkyl or the aryl that are selected from hydrogen, line style or branching, fatty acyl group, aroyl, alkoxyl group, aryloxy, alkylthio, dialkylamino, carbalkoxy, aryloxy carbonyl, formamyl, alkyl-or dialkyl-7-amino formyl radical, acyloxy, amido, aromatic acylamino, straight chain, side chain or cyclic alkylidene or its combination in one or more.In one preferred embodiment, substituent R has maximum 50 non-hydrogen atoms, and preferred 1 to 30 carbon also can be by replacements such as halogen or heteroatomss.The non-limitative example of alkyl substituent R comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl etc., comprises their all isomer, for example the tertiary butyl, sec.-propyl etc.Other alkyl comprise methyl fluoride, fluoro ethyl, two fluoro ethyls, iodine propyl group, bromine the organic quasi-metal base that replaces of base, benzyl chloride base and alkyl comprise trimethyl silyl, trimethylammonium germyl, methyl diethylsilane base etc.; The organic quasi-metal base that replaces with the halo alkyl comprises three (trifluoromethyl)-silyls, methyl-two (difluoromethyl) silyl, brooethyl dimethyl germyl etc.; Comprise for example dimethyl boron with dibasic boryl; Comprise dimethyl amine, dimethyl phosphine, diphenylamine, aminomethyl phenyl phosphine with dibasic pnicogen group; The chalcogen group comprises methoxyl group, oxyethyl group, propoxy-, phenoxy group, dimethyl sulfide and ethyl-sulfide.Non-hydrogen substituent R comprises atoms such as carbon, silicon, boron, aluminium, nitrogen, phosphorus, oxygen, tin, sulphur, germanium, comprises alkene as the unsaturated substituting group of (but being not limited to) olefinic, comprises the part of ethenyl blocking, for example fourth-3-thiazolinyl, third-2-thiazolinyl, own-5-thiazolinyl etc.And at least two R bases (preferred two adjacent R bases) link to each other and are formed with 3 to 30 ring structures that are selected from the atom of carbon, nitrogen, oxygen, phosphorus, silicon, germanium, aluminium, boron or its combination.And substituent R such as 1-butylene base (1-butanyl) can form carbon σ-key with metal M.

Other part can with the metal M bonding, as at least one leavings group Q.In one embodiment, Q is the unstable part of single anion that σ-key is arranged with M.The oxidation state that depends on described metal, the value of n are 0,1 or 2 so that following formula (III) is represented neutral big ligand metal cyclopentadienyl catalyst compound.

The non-limitative example of Q part comprises weak base such as amine, phosphine, ether, carboxylate radical, alkyl, hydride ion or halogen etc. or its combination of 1 to 20 carbon atom is arranged.In another embodiment, two or more Q constitutes the part of condensed ring or ring system.Other example of Q part comprises those substituting groups of R noted earlier, comprises cyclobutyl, cyclohexyl, heptyl, tolyl, trifluoromethyl, tetramethylene, pentamethylene, methylene radical, methoxyl group, oxyethyl group, propoxy-, phenoxy group, two (methylphenylamines), dimethylamino, diformazan phosphino-etc.

In one embodiment, the big ligand metal cyclopentadienyl catalyst of the present invention compound comprises wherein L ^AAnd L ^BBy formula (III) compound of the mutual bridging of at least one bridging group A, thereby be expressed from the next:

L ^AAL ^BMQ _n (IV)

Bridging compound shown in the formula (IV) is called the big ligand metal cyclopentadienyl catalyst compound of bridging.L ^A, L ^B, M, Q and n such as front define.The non-limitative example of bridging group A comprises the bridged group that contains at least one the 13rd to 16 family's atom that is commonly referred to divalent moiety, and for example (but being not limited to) carbon, oxygen, nitrogen, silicon, aluminium, boron, germanium and tin atom are one of at least or its combination.Preferred bridging group A contains carbon, silicon or germanium atom, and most preferably A contains at least one Siliciumatom or at least one carbon atom.Described bridging group A can also contain the defined substituent R in front, comprises halogen or iron.The non-limitative example of bridging group A can be expressed as R, ₂C, R, ₂Si, R, ₂SiR ' ₂Si, R ' ₂Ge, R ' P, R wherein, be the chalcogen or the halogen of alkyl, the halo alkyl of hydride ion, alkyl, replacement, the halo alkyl of replacement, the organic quasi-metal that alkyl replaces, the organic quasi-metal that the halo alkyl replaces, dibasic boron, dibasic pnicogen, replacement independently, perhaps two or more R can be linked to be ring or ring system.In one embodiment, the big ligand metal cyclopentadienyl catalyst of the bridging compound of formula (IV) has two or more bridging group A (EP 664 301B1).

In one embodiment, described big ligand metal cyclopentadienyl catalyst compound is formula (III) and big ligand L (IV) ^AAnd L ^BOn substituent R replaced by the substituting group of identical or different quantity on each big part those.In another embodiment, formula (III) and big ligand L (IV) ^AAnd L ^BDiffer from one another.

Be applicable to that other big ligand metal cyclopentadienyl catalyst compound of the present invention and catalyst system can comprise those described in the following document: US 5 064 802,5 145 819,5 149 819,5 243 001,5 239 022,5 276 208,5 296 434,5 321 106,5 329031,5 304 614,5 677 401,5 723 398,5 753 578,5 854 363,5 856 547,5 858 903,5 859 158,5 900 517 and 5 939 503, WO93/08221, WO93/08199, WO95/07140, WO98/11144, WO98/41530, WO98/41529, WO98/46650, WO99/02540, WO99/14221, EP-A-0 578 838, EP-A-0 638595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0632 819, EP-B1-0 748 821 and EP-B1-0 757 996 all are incorporated herein for reference.

In one embodiment, be applicable to that big ligand metal cyclopentadienyl catalyst of the present invention comprises the heteroatoms of bridging, single big ligand metal cyclopentadinyl compound.The catalyzer of these types and catalyst system for example be described in WO92/00333, WO94/07928, WO9I/04257, WO94/03506,96/00244, WO97/15602, WO99/20637 and US 505 7475,5 096 867,5 055 438,5 198 401,5 227 440 and 5 264 405 and EP-A-0 420 436 in, all be incorporated herein for reference.

In this embodiment, described big ligand metal cyclopentadienyl catalyst compound is expressed from the next:

L ^CAJMQ _n (V)

Wherein M is the 3rd to 16 family's atoms metal or the metal that is selected from periodic table of elements actinium series and group of the lanthanides, and preferred M is the 4th to 12 group 4 transition metal, and more preferably M is the 4th, 5 or 6 group 4 transition metals, and most preferably M is the 4th group 4 transition metal, particularly titanium of any oxidation state; L ^CFor with the replacement or the unsubstituted big part of M bonding; J and M bonding; A and M and J bonding; J is the heteroatoms assistant ligand; A is a bridging group; Q is the univalent anion part; With n be 0,1 or 2 integer.In the top formula V, L ^C, A becomes the condensed ring system with J-shaped.In one embodiment, the L of formula V ^CAs the front at L ^ADefine, the A of formula V, M and Q in the front formula (III) definition.

In the formula V, J is for containing heteroatomic part, and wherein J is that ligancy is that 3 the 15th family's element or ligancy are the 16th family's element of 2.Preferred J contains nitrogen, phosphorus, oxygen or sulphur atom, nitrogen.

In the one embodiment of this invention, the luxuriant type catalyst compound of described big ligand metal is the heterocyclic ligand title complex, and wherein said big part (ring or ring system) comprises one or more heteroatoms or its combination.Heteroatomic non-limitative example comprises the 13rd to 16 family's element, preferred nitrogen, boron, sulphur, oxygen, aluminium, silicon, phosphorus and tin.The example of these big ligand metal cyclopentadienyl catalyst compounds is described in WO96/33202, WO96/34021, WO97/17379, WO98/22486, EP-A1-0 874005 and US 5 637 660,5 539 124,5 554 775,5 756 611,5 233 049,5 744 417 and 5 856 258, all is incorporated herein for reference.

In one embodiment, described big ligand metal cyclopentadienyl catalyst compound is those title complexs that are called based on the transition-metal catalyst of the bidentate ligand that contains pyridine or quinoline moiety, described in the USSN 09/,103 620 of application on June 23rd, 1998 those are incorporated herein for reference.In another embodiment, described big ligand metal cyclopentadienyl catalyst compound is those described in WO99/01481 and the WO98/42664, all is incorporated herein for reference.

In another embodiment, described big part shaped metal cyclopentadienyl catalyst compound is the title complex of a kind of metal (preferred transition metal), big part (preferably replacing or unsubstituted π-key part) and one or more assorted allyl group part, as US 5 527 752 and 5 747 406 and EP-B1-O735 057 described in those, all be incorporated herein for reference.

Estimate as the USSN 09/,191 916 of application on November 13rd, 1998 described in, the big ligand metal cyclopentadienyl catalyst of the present invention compound arbitrary all has at least one fluorion or fluorine-containing leavings group.

In another embodiment, described another kind of metallic compound or second kind of metallic compound are big ligand metal cyclopentadienyl catalyst compounds shown in the following formula:

L ^DMQ ₂(YZ)X _n (VI)

Wherein M is the 3rd to 16 family's metal, preferred the 4th to 12 group 4 transition metal, most preferably the 4th, 5 or 6 group 4 transition metals; L ^DFor with the big part of M bonding; Each Q independently with M bonding, Q ₂(YZ) form part, preferred single electric charge polydentate ligand; A or Q be also with the univalent anion part of M bonding; When n is 2 X be the univalent anion base or when n is 1 X be the dianion base; N is 1 or 2.

In the formula (VI), L and M as the front to formula (III) definition.Q as the front to formula (III) definition, preferred Q is selected from-O-,-NR-,-CR ₂-and-S-; Y is C or S; Z is selected from-OR ,-NR ₂,-CR ₃,-SR ,-SiR ₃,-PR ₂,-H and replacement or unsubstituted aryl, condition are as Q during for-NR-, Z is selected from-OR ,-NR ₂,-SR ,-SiR ₃,-PR ₂, and-H; R is selected from the group of carbon containing, silicon, nitrogen, oxygen and/or phosphorus, and preferred R is the alkyl that contains 1 to 20 carbon atom, most preferably alkyl, cycloalkyl or aryl; N is 1 to 4 integer, preferred 1 or 2; When n is 2 X be the univalent anion base or when n is 1 X be the dianion base; Preferred X is carboxylamine root, carboxylate radical or described Q, Y and described other the assorted allyl group part of Z combination.

In one particularly preferred embodiment, described big ligand metal cyclopentadinyl compound is expressed from the next:

In hybrid catalyst system, above-mentioned first and second metallic compounds can 1:1000 to 1000:1, preferred 1:99 to 99:1, preferred 10:90 to 90:10, more preferably 20:80 to 80:20, more preferably 30:70 to 70:30, the more preferably mixed in molar ratio of 40:60 to 60:40.Selected ratio depends on the finished product of wanting and/or activation method.

Activator and activation method

Typically with the whole bag of tricks metallic compound activation described herein being produced has and will make the catalyst compound of the empty coordination valence of alkene coordination, insertion and polymeric position.

In patent specification and the appended claims, term " activator " is defined as any compound or the component or the method for the metallic compound that can make the present invention as previously described contain the 15th family's element and/or big ligand metal cyclopentadienyl catalyst compound activating.For example, nonrestrictive activator can comprise that metallic compound that Lewis acid or non-coordination ion activator or ionization activator maybe can make neutral big ligand metal cyclopentadienyl catalyst compound or contain the 15th family's element changes into the metallic compound that contains the 15th family's element or big luxuriant cationic any other compound of ligand metal of catalytic activity, comprises Lewis base, aluminum alkyls, traditional promotor and combination thereof.Make activator and/or also with big ligand metal cyclopentadienyl catalyst of described neutrality and/or the described ionized ionization activator of metallic compound (neutrality or ion) that contains the 15th family's element are made up also within the scope of the present invention as four (pentafluorophenyl group) boric acid, three positive fourth ammoniums, three perfluorophenyl boron metalloid precursors or three perfluor naphthyl boron metalloid precursors, the assorted borine negatively charged ion (WO98/43983) of many halos or its with aikyiaiurnirsoxan beta or modified alumoxane.

In one embodiment, comprise also that use does not contain active proton but can produce the metallic compound positively charged ion that contains the 15th family's element or the activation method of the ionization ionic compound of big ligand metal cyclopentadienyl catalyst positively charged ion and non-coordination anion thereof, be described among EP-A-0 426 637, EP-A-0 573403 and the US 5 387 568, all be incorporated herein for reference.

The preparation method that many kinds of aikyiaiurnirsoxan beta and modified alumoxane are arranged, its non-limitative example is described in US 4 665 208,4 952 540,5 091 352,5 206 199,5 204 419,4 874 734,4 924 018,4 908 463,4 968 827,5 308 815,5 329032,5 248 801,5 235 081,5 157 137,5 103 031,5 391 793,5 391 529,5 693 838,5 731 253,5 731 451,5 744 656,5 847177,5 854 166,5 856 256 and 5 939 346, EP-A-0 561 476, EP-B1-0279 586, EP-A-0 594 218, among EP-B1-0 586 665 and the WO94/10180, all be incorporated herein for reference.

The organo-aluminium compound that is suitable as activator comprises trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium etc.

The ionization compound can contain active proton or associate with the residual ion of described ionization compound but not coordination or only loose with it some other positively charged ion of coordinate with it.This compounds etc. is described among the USSN 08/,285 380 that EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0500 944, EP-A-0 277 003, EP-A-0 277 004, US apply for 5 153 157,5 198401,5 066 741,5 206 197,5 241 025,5 384 299 and 5 502 124 and 1994 on Augusts 3,, all is incorporated herein for reference.

Other activator comprises those described in the WO98/07515, and as three (2,2,, 2, ,-nine fluorine xenyls) and the fluoro aluminate, be incorporated herein for reference.The present invention also comprises the combination of activator, and for example aikyiaiurnirsoxan beta and ionization activator combination referring to for example EP-B1-0 573 120, WO94/07928, WO95/14044, US 5 153 157 and 5 453 410, all is incorporated herein for reference.WO98/09996 (being incorporated herein for reference) describes and makes big ligand metal cyclopentadienyl catalyst compound activating with perchlorate, periodate and iodate (comprising its hydrate).WO98/30602 and WO98/30603 (being incorporated herein for reference) describe with (2,2 ,-xenyl-two-trimethylammonium silicic acid) lithium 4THF and make the activator of big ligand metal cyclopentadienyl catalyst compound.WO99/18135 (being incorporated herein for reference) describes and uses organic boron-aluminium activator.EP-B1-0781 299 describes with the compatible negatively charged ion combination with non-coordination of silicon salt.Also comprise with activation methods such as radiation (, being incorporated herein for reference), electrochemical oxidations as making described neutrality big ligand metal cyclopentadienyl catalyst compound or precursor conversion become the luxuriant cationic activation method of big ligand metal of energy olefin polymerization referring to EP-B1-0 615 981.Other activator or the activation method that are used for big ligand metal cyclopentadienyl catalyst compound are described in for example US 5 849 852,5 859 653 and 5 869723, WO98/32775, WO99/42467 (two (three (pentafluorophenyl group) borine) benzimidazolines of two (octadecyl) ammonium methyl), all are incorporated herein for reference.

In one embodiment, described activator is a lewis acid compound, more preferably aluminium base lewis acid compound most preferably has at least one (preferred two) halogenated aryl part and one or two neutral aluminium base lewis acid compound that does not comprise other single anion ligand of halogenated aryl part.The lewis acid compound of this embodiment includes at least one huge electrophilic assistant ligand those olefin polymerization catalysis activator Lewis acids based on aluminium as the halogenated aryl part of three (perfluorophenyl) borines or three (perfluor naphthyl) borine.These huge assistant ligands are to be enough to make described Lewis acid to play those of the stable compatible non-coordination anion effect of electronics.Described negatively charged ion is not that part that the strong lewis acid that is suitable for being used for insertion polymerization contains the transition-metal cation of the 15th family's element obtains stable ionic complex when giving body, promptly suppresses neutralize described positively charged ion and makes it part transfer to the polymerization non-activity.

The Lewis acid that meets this description of this preferred active agent can be expressed from the next:

R _nAl(ArHal) _3-n (VII)

Wherein R is a single anion ligand, and ArHal is halogenated C ₆The polycyclic aromatic hydrocarbons of aromatic hydrocarbons or higher carbon number or two or more ring (or condensing ring system) aromatic ring system that directly interconnects or link together wherein, n=1 to 2, preferred n=1.

In another embodiment, formula (VII) at least one (ArHal) is halogenated C ₉Aromatic hydrocarbons or higher, preferred fluoro naphthyl.The non-limiting R part that is suitable for comprises: replace or unsubstituted C ₁To C ₃₀Aliphatic series or aromatic hydrocarbyl, at least one hydrogen that means on the carbon atom of replacement is replaced by following substituting group: organic quasi-metal, dialkylamino, alkoxyl group, siloxy, aryloxy, alkylthio, arylthio, alkane phosphino-, alkane phosphino-or other anion substituent that alkyl, halogen, halo alkyl, alkyl or halo alkyl replace; Fluorine; Huge pure root, the wherein huge C that means ₄The alkyl of higher carbon number (for example the highest about C ₂₀), as trimethyl carbinol root, 2,6-dimethyl-phenol root and 2,6-di-tert-butylphenol root;-SR;-NR ₂And-PR ₂, wherein each R is defined replacement in front or unsubstituting hydrocarbyl independently; And C ₁To C ₃₀Organic quasi-metal such as trimethyl silyl that alkyl replaces.

Phenyl, naphthyl and the anthryl of US5 198 401 when the example of ArHal comprises by halo and the xenyl of WO97/29845.Term halo or halogenation mean that 1/3 hydrogen atom is replaced by halogen atom on the carbon atom of aromatic ligand of described aryl-replacement among the application, and more preferably described aromatic ligand is by perhalogeno.Fluorine is most preferred halogen.

In another embodiment, in the scope of mol ratio between 0.3:1 to 1000:1 of the metal of the catalyst compound that contains the 15th family's element of the metal of described activator component and described load, preferred 20:1 to 800:1, most preferably 50:1 to 500:1.Described activator is the ionization activator as based on those of four (pentafluorophenyl group) boron anion the time, and the mol ratio of the metal group branch of the metal of described activator component and the described hafnium catalyst compound that contains the 15th family's element is preferably in the scope between 0.3:1 to 3:1.

Above-mentioned metallic compound that contains the 15th family's element and/or described big ligand metal cyclopentadienyl catalyst compound can combine also within the scope of the invention with catalyst compound shown in one or more formula (III) to (VI) and one or more above-mentioned activator or activation method.

In another embodiment of described mixed catalyst composition, modified alumoxane is combined with the present invention's first and second metallic compounds form catalyst system.In another embodiment, make the MMAO3A (n-heptane solution of modified methylaluminoxane, available from Akzo Chemicals, Inc., Holland, trade(brand)name Modified Methylalumoxane type 3A referring to disclosed those aikyiaiurnirsoxan beta among the US5041 584 for example, is incorporated herein for reference) combine with described first and second metallic compounds and form catalyst system.

In one particular embodiment, when using metallic compound shown in identical activator activatory formula 1 and the formula 2, preferred weight percentage based on these two kinds of metallic compound weight (not comprising activator or any carrier) is compound of 10 to 95% (weight) formula 1 and the compound of 5 to 90% (weight) formula 2, compound of preferred 50 to 90% (weight) formula 1 and the compound of 10 to 50% (weight) formula 2, the more preferably compound of the compound of 60 to 80% (weight) formula 1 and 40 to 20% (weight) formula 2.In one particularly preferred embodiment, make the compound activating of formula 2, then with the compound chemical combination of formula 2, in the reactor that reinjects with methylaluminoxane.

In one particular embodiment, when using identical activator activatory Compound I and three PIVALIC ACID CRUDE (25) indenyls to close zirconium, preferred weight percentage based on these two kinds of catalyst weights (not comprising activator or any carrier) is that 10 to 95% (weight) Compound I and 5 to 90% (weight) three PIVALIC ACID CRUDE (25) indenyls close zirconium, preferred 50 to 90% (weight) Compound I and 10 to 50% (weight) three PIVALIC ACID CRUDE (25) indenyls close zirconium, and more preferably 60 to 80% (weight) Compound I and 40 to 20% (weight) three PIVALIC ACID CRUDE (25) indenyls close zirconium.In one particularly preferred embodiment, make three PIVALIC ACID CRUDE (25) indenyls close the zirconium activation with methylaluminoxane, then with Compound I chemical combination, in the reactor that reinjects.

Usually, described bonded metallic compound and activator are with the ratio chemical combination of about 1000:1 to about 0.5:1.In one preferred embodiment, metallic compound and activator with about 300:1 to about 1:1, preferred about 150:1 ratio chemical combination of about 1:1 extremely, for borine, borate, aluminate etc., described ratio is preferably about 1:1 to about 10:1, for alkylaluminium cpd (as with water bonded diethylaluminum chloride) for, described ratio is preferably about 0.5:1 to about 10:1.

Traditional catalyst system

Mixed catalyst composition of the present invention also can comprise the metallic compound of the 15th family's element and the traditional transition-metal catalyst of containing noted earlier.

Traditional transition-metal catalyst is those traditional Z-Ns well known in the art, vanadium and Philips-type catalyzer.Ziegler-Natta Catalysts andPolymerization for example, John Boor, Academic Press, New York, Ziegler-natta catalyst described in 1979.The example of conventional transition metal catalyst also is described in US 4,115 639,4 077 904,4 482 687,4 564 605,4 721 763,4 879 359 and 4 960 741, all is incorporated herein for reference.Can be used for conventional transition metal catalyst compounds of the present invention comprises from the periodic table of elements the 3rd to 17 family, preferred the 4th to 12 family, the more preferably transistion metal compound of 4 to 6 families.

These traditional transition-metal catalysts can be expressed from the next: MR _x, wherein M is the 3rd to 17 family's metal, preferred the 4th to 6 family's metal, more preferably group-4 metal, titanium most preferably; R is halogen or-oxyl; X is the oxidation state of metal M.The non-limitative example of R comprises alkoxyl group, phenoxy group, bromine, chlorine and fluorine.Wherein M is that the non-limitative example of the conventional transition metal catalyst of titanium comprises TiCl ₄, TiBr ₄, Ti (OC ₂H ₅) ₃Cl, Ti (OC ₂H ₅) Cl ₃, Ti (OC ₄H ₉) ₃Cl, Ti (OC ₃H ₇) ₂Cl ₂, Ti (OC ₂H ₅) ₂Br ₂, TiCl ₃1/3AlCl ₃And Ti (OC ₁₂H ₂₅) Cl ₃

Be applicable to and of the present inventionly for example be described among the US 4 302 565 and 4 302 566 for the conventional transition metal catalyst compounds of electronics title complex, be incorporated herein for reference based on magnesium/titanium.Preferred especially MgTiCl ₆(ethyl acetate) ₄Derivative.

GB 2 105 355 and US 5 317 036 (being incorporated herein for reference) have described multiple traditional vanadium catalyst compound.The non-limitative example of tradition vanadium catalyst compound comprises three halogenations, alkoxyl group halogenation and alkoxylate vanadyl such as VOCl ₃, VOCl ₂(OBu) (wherein Bu=butyl) and VO (OC ₂H ₅) ₃Four halogenation vanadium and alkoxyl group halogenation vanadium such as VCl ₄And VCl ₃(OBu); Methyl ethyl diketone and chloracetyl acetonization vanadium and vanadyl such as V (AcAc) ₃And VOCl ₂(AcAc) (wherein (AcAc) is methyl ethyl diketone).Preferred traditional vanadium catalyst compound is VOCl ₃, VCl ₄And VOCl ₂-OR, wherein R is an alkyl, preferred C ₁To C ₁₀Aliphatic series or aromatic hydrocarbyl such as ethyl, phenyl, sec.-propyl, butyl, propyl group, normal-butyl, isobutyl-, the tertiary butyl, hexyl, cyclohexyl, naphthyl etc. and acetylacetonate vanadium.

Be applicable to that traditional chrome catalysts compound of the present invention (being commonly referred to Philips's type catalyzer) comprises CrO ₃, two luxuriant chromium, silyl chromate, chlorination oxygen chromium (CrO ₂Cl ₂), 2 ethyl hexanoic acid chromium, acetylacetonate chromium (Cr (AcAc) ₃) etc.Non-limitative example is disclosed in US 3 709853,3 709 954,3 231 550,3 242 099 and 4 077 904, all is incorporated herein for reference.

Be applicable to that other conventional transition metal catalyst compounds of the present invention and catalyst system are disclosed among US 4 124 532,4 302 565,4 302 566,4 376 062,4 379 758,5 066 737,5 763 723,5 849 655,5 852 144,5 854 164 and 5 869585, EP-A2-0 416 815A2 and the EP-A1-0 420 436, all are incorporated herein for reference.

Other catalyzer can comprise cationic catalyst such as AlCl ₃With other cobalt well known in the art, iron, nickel and palladium catalyst.Referring to for example US 3 487 112,4 472 559,4 182 814 and 4 689 437, all be incorporated herein for reference.

These traditional transition metal catalyst compound typically activate with one or more following traditional promotor except that some traditional chrome catalysts compounds.As is known to the person skilled in the art, above-mentioned activator activation in the also available patent specification of traditional transition-metal catalyst.

The traditional cocatalyst compound that is used for above-mentioned traditional transition metal catalyst compound can be expressed from the next: M ³M ⁴ _vX ² _cR ³ _B-c, M wherein ³Be the periodic table of elements the 1st to 3 family and 12 to 13 family's metals; M ⁴Be the periodic table of elements the 1st family's metal; V is 0 to 1 number; Each X ²Be any halogen; C is 0 to 3 number; Each R ³Be monovalence alkyl or hydrogen; B is 1 to 4 number; B-c is at least 1.Other the traditional organo-metallic cocatalyst compound that is used for above-mentioned conventional transition metal catalyst has following formula: M ³R ³ _k, M wherein ³Be IA, IIA, IIB or IIIA family metal, as lithium, sodium, beryllium, barium, boron, aluminium, zinc, cadmium and gallium; K equals 1,2 or 3, depends on M ³Valency, its valency depends on M usually again ³Affiliated family; Each R ³It can be any monovalence alkyl.

The non-limitative example that is applicable to traditional organo-metallic cocatalyst compound of above-mentioned conventional catalyst immunomodulator compounds comprises lithium methide, the basic mercury of butyllithium, two, dibutyl magnesium, diethyl cadmium, benzyl potassium, zinc ethyl, three n-butylaluminum, diisobutyl ethyl boron, diethyl cadmium, di-n-butyl zinc and three n-pentyl boron, aluminum alkyls particularly is as three hexyl aluminium, triethyl aluminum, trimethyl aluminium and triisobutyl aluminium.Other traditional cocatalyst compound comprises one of Organohalogen compounds of group II metal and hydride and the 3rd and 13 family's metals-or two-Organohalogen compounds and hydride.The non-limitative example of this traditional cocatalyst compound comprises bromination diisobutyl aluminum, isobutyl dichloride boron, methylmagnesium-chloride, tonsilon beryllium, bromination ethyl calcium, diisobutylaluminium hydride, hydrogenation methyl cadmium, hydrogenation diethyl boron, hydrogenation hexyl beryllium, hydrogenation dipropyl boron, hydrogenation octyl group magnesium, hydrogenation butyl zinc, hydrogenation dichloro boron, hydrogenation dibromo aluminium and hydrogenation bromine cadmium.Traditional organo-metallic cocatalyst compound is known in the art, and the visible US 3 221 002 of the more detailed argumentation of these compounds and 5 093 415 all is incorporated herein for reference.

Carrier and general load technology

Make one of in the available known in this field or following described carrying method and above-mentionedly contain the catalyzer of the 15th family's element and/or comprise that the described catalyst compound that contains the 15th family's element combines with one or more solid support material or carrier with the hybrid catalyst system of described big ligand metal cyclopentadienyl catalyst compound or conventional catalyst immunomodulator compounds.In one embodiment, catalyzer that contains the 15th family's element of the present invention or described hybrid catalyst system are its load form, for example be deposited on the carrier, with carrier contact, vaporize with carrier, with the carrier bonding or mix, adsorb or be absorbed in the carrier.When being used for mixed system, described big ligand metal cyclopentadienyl catalyst is carried on the carrier different with the described catalyzer that contains the 15th family's element also within the scope of the present invention, is specially adapted to wherein produce high molecular weight component with a kind of load type catalyst system in a reactor and the situation of producing the reactor system of lower-molecular-weight component with another kind of load type catalyst system in another reactor.

Term " carrier " is any solid support material, and preferred porous carrier materials comprises inorganic or organic support material.The non-limitative example of inorganic carrier material comprises inorganic oxide and butter.Other carrier comprises resinous support material such as polystyrene, functionalized or crosslinked organic carrier such as polystyrene divinylbenzene polyolefine or polymerizable compound or other any organic or inorganic solid support material etc., or its mixture.

Preferred carrier is an inorganic oxide, comprises those the 2nd, 3,4,5,13 or 14 family metal oxides.Preferred carrier comprise silicon oxide, aluminum oxide, silica-alumina, and composition thereof.Other carrier that is suitable for comprises magnesium oxide, titanium oxide, zirconium white, magnesium chloride, montmorillonite (EP-B1-0 511 665), phyllosilicate, zeolite, talcum and clay etc.The mixture of these solid support materials also can use, for example silicon oxide-chromium, silica-alumina, silicon oxide-titanium oxide etc.Other solid support material can comprise those porous propylene acids polymkeric substance described in EP 0 767 184 B1, is incorporated herein for reference.

The surface-area of preferred described carrier (most preferably inorganic oxide) about 10 to about 100m ²In the scope of/g, pore volume in about scope of 0.1 to about 4.0cc/g, mean particle size about 5 to the scope of about 500 μ m.More preferably the surface-area of described carrier about 50 to about 500m ²In the scope of/g, pore volume in about scope of 0.5 to about 3.5cc/g, mean particle size about 10 to the scope of about 200 μ m.Most preferably the surface-area of described carrier is in about scope of 100 to about 400m2/g, pore volume in about scope of 0.8 to about 5.0cc/g, mean particle size about 5 to the scope of about 100 μ m.The mean pore size of carrier of the present invention typically is 10 to 1000 in the aperture

Scope in, preferred 50 to about 500

, most preferably 75 to about 450

The example of supported catalyst of the present invention is described in US 4 701 432,4 808 561,4 912075,4 925 821,4 937 217,5 008 228,5 238 892,5 240 894,5 332 706,5 346 925,5 422 325,5 466 649,5 466 766,5 468702,5 529 965,5 554 704,5 629 253,5 639 835,5 625 015,5 643 847,5 665 665,5 698 487,5 714 424,5 723 400,5 723402,5 731 261,5 759 940,5 767 032,5 770 664,5 846 895 and 5 939 348, USSN 271 598 (1994.07.07 application) and 788 736 (1997.01.23 applications), WO95/32995, WO95/14044, WO96/06187, WO97/02297, among the EP-B1-0685494, all be incorporated herein for reference.

This area has many other methods to be used for polymerization catalyzed immunomodulator compounds of load the present invention or hybrid catalyst system.For example, describedly contain the catalyst compound of the 15th family's element and/or comprise that the hybrid catalyst system of big ligand metal cyclopentadienyl catalyst compound can contain the part of polymer-bound described in the US 5 473 202 and 5,770 755 (being incorporated herein for reference); Catalyst compound and/or the big ligand metal cyclopentadienyl catalyst compound that contains the 15th family's element of the present invention can be as spraying drying described in the US5 648 310 (being incorporated herein for reference); The carrier that is used for metal catalyst compounds that contains the 15th family's element of the present invention and/or big ligand metal cyclopentadienyl catalyst compound can be functionalized described in EP-A-0 802 203 (being incorporated herein for reference); Or described in US5 688 880 (being incorporated herein for reference), select at least one substituting group or leavings group.

In another embodiment, the invention provides a kind of mixed system that contains the catalyst system of the 15th family's element and/or comprise big ligand metal cyclopentadienyl catalyst compound, comprise the surface-modifying agent that described in WO96/11960 (being incorporated herein for reference), is used to prepare load type catalyst system.Catalyst system of the present invention can for example prepare in the presence of the hexene-1 at alkene.

In another embodiment, the described hafnium catalyst system that contains the 15th family's element and comprise the mixed system of big ligand metal cyclopentadienyl catalyst compound can be described in USSN 09/,113 216 (1998.07.10 application) with metal carboxylate for example ALUMINUM CARBOXYLIC as one-, two-and three-aluminum stearate, sad, oleic acid and cyclohexyl butyric acid calorize close.

The production method that loading type contains the catalyst system and/or the big ligand metal ocene catalyst system of the 15th family's element is described below, be described among USSN 265 533 (1994.06.24 application) and 265 532 (1994.06.24 applications), WO96/00245 and the WO96/00243 (1996.01.04 is open), all be incorporated herein for reference.This method is used for the arbitrary of described catalyst compound that contains the 15th family's element or described big ligand metal cyclopentadienyl catalyst compound or both.In this method, catalyst compound is suspended in forms solution in the liquid, preparation contains another solution of activator and liquid.Described liquid can be any compatible solvent or other liquid that can form solution etc. with catalyst compound of the present invention and/or activator.In one preferred embodiment, described liquid is cyclic aliphatic or aromatic hydrocarbon, most preferably toluene.Described catalyst compound solution and activator solution are mixed, add the cumulative volume that makes catalyst compound solution and activator solution in the porous support and be lower than 4 times of pore volume of described porous support, more preferably less than 3 times, even more preferably less than 2 times; Preferably in 1.1 to 3.5 times scope, most preferably in 1.2 to 3 times scope.

The measuring method of the total pore volume of porous support is known in this field.Volume 1, and Exprimental Methods in Catalytic Research (Academic Press, 1968) (especially referring to the 67-96 page or leaf) has discussed one of these methods in detail.This preferred method relates to the BET nitrogen adsorption unit that uses classics.Another kind of method well known in the art is described in Innes, Total Porosity and Particle Density of Fluid CatalystsBy Liquid Titration, Vol.28, No.3, among the Analytical Chemistry332-334 (March, 1956).

Other method of load catalyst compound of the present invention is described in USSN 09/,312 878 (1999.05.17 application), is incorporated herein for reference.

When being used for hybrid catalyst system, catalyst compound that contains the 15th family's element of the present invention and big ligand metal cyclopentadienyl catalyst compound are with 1:1000 to 1000:1, preferred 1:99 to 99:1, preferred 10:90 to 90:10, more preferably 20:80 to 80:20, more preferably 30:70 to 70:30, the more preferably mixed in molar ratio of 40:60 to 60:40.

In one of mixed system of the present invention embodiment, particularly in slurry polymerization process, contain the compound of the 15th family's element and the dead weight capacity of big ligand metal cyclopentadienyl catalyst compound and be expressed as about 40 μ mmol/g, preferably about 38mmol/g with the final loaded catalyst of μ mmol/g (comprising solid support material, mixed catalyst and activator).

In another embodiment, particularly in the gaseous polymerization of using mixed system of the present invention, the dead weight capacity that contains the compound of the 15th family's element and big ligand metal cyclopentadienyl catalyst compound is expressed as with the final loaded catalyst of μ mmol/g (comprising solid support material, mixed catalyst and activator) and is lower than about 30 μ mol/g, preferably be lower than about 25 μ mmol/g, more preferably less than 20 μ mmol/g.

In another embodiment, above the R base of formula (VII) or part can with solid support material preferable alloy/quasi-metal oxide or polymeric carrier covalent bonding.The solid support material or the matrix that contain Lewis base will be reacted the lewis acid compound (loading type activator) that forms with the carrier bonding, wherein R with described Lewis acid activation agent _nAl (ArHal) _3-nR base and solid support material covalent bonding.For example, when solid support material was silicon oxide, the Lewis base hydroxyl of silicon oxide was the position that bonding takes place in one of aluminium coordination valence position in this method.In this embodiment, preferred described solid support material is metal or quasi-metal oxide, preferably has surface hydroxyl, pK _aBe equal to or less than the pK of amorphous silicon oxide _a, i.e. pK _aBe less than or equal to about 11.

Do not wish to be bound by any theory, believe the anion active agent (Lewis acid) of described covalent bonding initial with silanol group for example (as the Lewis base) of silicon oxide form the coordination valence title complex, thereby form and the metal of described metal oxide carrier or formal the two poles of the earth (zwitter-ion) Bronsted acid structure of metalloid bonding.As if then, the proton of described Bronsted acid makes described lewis acidic R-base protonated (capturing it), this moment, described Lewis acid became and described Sauerstoffatom covalent bonding.Replace described lewis acidic R base then and become R ,-O-, wherein R ' is solid support material or the matrix that is fit to, for example polymeric carrier of silicon oxide or hydroxyl.Any solid support material that contains surface hydroxyl all is applicable to this special carrying method.Other solid support material comprises granulated glass sphere.

In this embodiment, when described solid support material was metal oxide composition, these compositions can also contain the oxide compound of other metal, as Al, K, Mg, Na, Si, Ti and Zr, preferably handled to remove by heat and/or chemical means and anhydrated and free oxygen.This handles typically in vacuum furnace, in the fluidized-bed of heating or with dewatering agent such as organic silane, siloxanes, alkylaluminium cpd etc.Described processing should be removed most of residual moisture and oxygen as much as possible, but keeps great amount of hydroxy group functional group.Therefore, can be up to 800 ℃ or decompose up to described solid support material before roasting temperature allowed in several hours, if negate carries more high-load anion active agent, then be adapted at the lower roasting temperature short period.When metal oxide is silicon oxide, typically reaches and be lower than 0.1 to 3.0mmol activator/g SiO ₂Load be fit to, can realize by for example in 200 to 800+ ℃ of scopes, changing maturing temperature.Referring to Zhuralev, etal.Langmuir 1987, Vol.3, and 316, the relation between the hydroxy radical content of silicon oxide of maturing temperature and time and different table area has wherein been described.

Also can before adding Lewis acid, can be used as the hydroxyl that adheres to the position with substoichiometric chemical dehydrator pre-treatment customization.Preferred use be have can with silanol group ((CH for example ₃) ₃SiCl) reaction or hydrolyzable single part are with extremely minimum those of the reaction that reduces to disturb transition metal catalyst compound and described bonding activator.Be lower than 400 ℃ maturing temperature if adopt, available difunctionality coupling agent ((CH for example ₃) ₂SiCl ₂) give the hydrogen bond of the silanol group that exists under the not harsh roasting condition to end-blocking.Referring to for example " Investigation ofQuantitative SiOH Determination by the Silane Treatment ofDisperse Silica ", Gorski, et al., Journ of Colloid and InterfaceScience, Vol.126, No.2, Dec.1988 also will make the silanol group modification on the support of the catalyst of the present invention effectively about the discussion of silane coupling agent to the influence of silicon oxide polymerization filling.Similarly, use to surpass with described transistion metal compound and react the required stoichiometric Lewis acid excessive silanol group that will neutralize, Preparation of catalysts or follow-up polymerization are not had significant adverse to be influenced.

Polymeric carrier is preferably the polymeric matrices of hydroxy functional groups, but functional group can be any primary alkyl amine, secondary alkylamine etc., wherein said group structurally mixes in the polymeric chain, can make the part of a coordination valence position that accounts for described aluminium protonated with described Lewis acid generation acid-alkali reaction, and be mixed with the polymkeric substance replacement of functional group.The polymkeric substance that contains functional group referring to for example US 5 288 677 is incorporated herein for reference.

Other carrier comprises silicon oxide, aluminum oxide, silica-alumina, magnesium oxide, titanium oxide, zirconium white, magnesium chloride, montmorillonite, phyllosilicate, zeolite, talcum, clay, silicon oxide-chromium, silica-alumina, silicon oxide-titanium oxide, porous propylene acid polymer.

In another embodiment of the present invention, before main polymerization, make alkene, preferred C ₂To C ₃₀Alkene or alpha-olefin, optimal ethylene or propylene or its mixture contain pre-polymerization in the presence of the metal catalyst of the 15th family's element and/or the big ligand metal cyclopentadienyl catalyst at loading type of the present invention.Described pre-polymerization can or be carried out continuously at gas phase, solution phase or slurry phase (be included in and boost down) intermittence.Described pre-polymerization can and/or be carried out in the presence of any molecular weight regulator such as hydrogen with any olefinic monomer or mixture.For example, all be incorporated herein for reference referring to the Prepolymerizing process of US 4 748 221,4789359,4923833,4921825,5283278 and 5705578, EP-B-0279863 and WO97/44371.

The solution feed that contains the compound of the 15th family's metallic element

In another embodiment, metal catalyst compounds and the activator that contains the 15th family's element of the present invention adds slurry or Gas-phase reactor in carrier fluid (preferred solution).Catalyzer and activator can infeed dividually or together, can mix before the next-door neighbour enters reactor, also can contact for a long time before entering reactor.Preferred carrier fluid comprises paraffinic hydrocarbons, preferred pentane, hexane, iso-pentane, toluene, hexanaphthene, iso-pentane, heptane, octane, isohexane etc.Particularly preferred carrier fluid comprises hexane, pentane, iso-pentane and toluene.

Described catalyst system, metallic compound and/or activator preferably add reactor in one or more solution.In one embodiment, the solution of activatory metallic compound in paraffinic hydrocarbons such as pentane, hexane, toluene or iso-pentane etc. is added gas phase or sludge phase reactor.In another embodiment, catalyst system or component can add reactor in suspension or emulsion.In one embodiment, transistion metal compound is contacted with activator such as modified methylaluminoxane in solvent, then solution is infeeded gas phase or sludge phase reactor.In another embodiment, solution of metal compound is mixed with the solution of activator, make it to react for some time, add reactor then.In one preferred embodiment, before adding reactor, make catalyzer and activator reaction at least 1 second, preferably at least 5 minutes even more preferably between 5 and 60 minutes.Catalyzer and the activator concentration that exists in solution typically is 0.0001-0.200mol/l, preferred 0.001-0.05mol/l, more preferably 0.005-0.025mol/l.Usually, the ratio of mixture of metallic compound and activator is that about 1000:1 is to about 0.5:1.In one preferred embodiment, the ratio of mixture of metallic compound and activator is that about 300:1 is to about 1:1, preferred about 10:1 is to about 1:1, for borine, this is than being preferably about 1:1 to about 10:1, for aluminum alkyls (as with water blended diethylaluminum chloride) for, this is than being preferably about 0.5:1 to about 10:1.

In another embodiment, the catalyst system of being made up of transistion metal compound (catalyzer) and/or activator (promotor) preferably adds reactor in solution.Solution of metal compound is preferably by making catalyzer be dissolved in preparation in any solvent such as paraffinic hydrocarbons, toluene, the dimethylbenzene etc.Described solvent can first purifying to remove any poisonous substance that may influence catalyst activity, comprise the water and/or the oxygenatedchemicals of any trace.The purifying of solvent can be finished with for example activated alumina and activatory carried copper catalyzer.Catalyzer is dissolved in fully forms homogeneous phase solution in the solution.Can make catalyzer and activator be dissolved in same solvent when needing.After catalyzer is dissolved in solution, can store until use.

For polymerization, preferably before injecting reactor, make catalyzer and activator mix.In addition, can in catalyst solution (online or off-line), activator (online or off-line) or activatory catalyzer, add other solvent and reactant.

In one preferred embodiment, the productive rate of catalyst system of the present invention is 10000g polymkeric substance/g catalyzer/hr or higher.

Catalyst system solution feed of the present invention as mentioned above has fabulous operability under the reactor condition of wide region, to the 3dg/min melt index, density is 0.950-0.916g/cc to resin grades from the 0.2dg/min flow index.Trial run any resin agglomeration do not occur in 10 days or hardens during described catalyst body tied up to continuously.The present invention does not almost have or does not have the benefit of fouling in addition.During polymerization technique or do not observe sheet, piece or rubble afterwards.The sign that does not have accumulation of polymer on the reactor wall or in the recycle gas line.And the pressure drop of passing interchanger, circulating air compressor or gas distribution grid during the whole test does not increase.

The solution feed of hybrid catalyst system

In another embodiment, hybrid catalyst system of the present invention and/or activator (promotor) add reactor in solution.Make described catalyzer be dissolved in preparation solution of metal compound in any suitable solvent such as paraffinic hydrocarbons, toluene, the dimethylbenzene etc.Described solvent can first purifying to remove any poisonous substance that may influence catalyst activity, comprise the water and/or the oxygenatedchemicals of any trace.The purifying of solvent can be finished with for example activated alumina and activatory carried copper catalyzer.Catalyzer is dissolved in fully forms homogeneous phase solution in the solution.Can make two kinds of catalyzer be dissolved in same solvent when needing.After catalyzer is dissolved in solution, but standing storage is until use.

For polymerization, preferably before injecting reactor, make catalyzer and activator mix.In addition, can in catalyst solution (online or off-line), activator (online or off-line) or activatory catalyzer, add other solvent and reactant.Described the solution feed system of supply response device referring to US5317036 and 5693727, EP-A-0593083 and WO97/46599, all be incorporated herein for reference.There are many different layouts can make catalyzer and activator mix.

Described catalyst system, metallic compound and/or activator can add reactor in one or more solution.Can make the metallic compound activation in succession independently, also can activate together.In one embodiment, the solution of two kinds of activatory metallic compounds in paraffinic hydrocarbons such as pentane, hexane, toluene or iso-pentane etc. is added gas phase or sludge phase reactor.In another embodiment, described catalyst system or component can add reactor in suspension or emulsion.In another embodiment, described second metallic compound is contacted with activator such as modified methylaluminoxane in solvent, then solution is added gas phase, slurry phase or solution-phase reaction device.The described metal compound solution that contains the 15th family's element is mixed with the solution of described second compound and activator, add reactor then.

In the following example, A represents catalyzer or catalyst mixture, and B represents different catalyzer or catalyst mixture.A can be identical catalyzer with catalyst mixture among the B, but the ratio difference.In addition, notice that many ground can add other solvent or rare gas element.

Example 1: make A and B add the activator off-line and mix, add reactor then.Example 1 is shown among Fig. 1.

Example 2: A and B off-line are mixed.Online adding activator adds reactor then.Example 2 is shown among Fig. 2.

Example 3: A or B are contacted, then online adding A or B before entering reactor with activator (off-line).Example 3 is shown among Fig. 3.

Example 4: A or B are contacted, then online adding A or B before entering reactor with activator (online).Example 4 is shown among Fig. 4.

Example 5: A is all contacted with the activator off-line with B.A is contacted with activator is online with B with activator.Example 5 is shown among Fig. 5.

Example 6: A is all contacted with activator is online with B.A is contacted with activator is online with B with activator.(this is a kind of preferred layout, because can control the ratio of A/B, the ratio of activator/A and the ratio of activator/B independently.) example 6 is shown among Fig. 6.

Example 7: in this example, make A or B contact (online) with activator, A separately or the solution of B are contacted with the activator off-line.Before entering reactor, make two liquid of A or B and activator flow online the contact then.Example 7 is shown among Fig. 7.

Example 8: make that A and B are online to be contacted.Online adding activator in described A and B mixture then.Example 8 is shown among Fig. 8.

Example 9: off-line makes the A activation with activator.Make then that A and activator are online to be contacted with B.Online adding activator in described A and B and activating mixtures.Example 9 is shown among Fig. 9.

Above in any example, can use and mix and/or produce the device of certain residence time.For example, available oar formula or mixing screw mix the contact or the residence time that requires between the pipe acquisition component of described component or available certain-length." online " mean described material with pipeline or container that reactor assembly directly or indirectly links to each other in." off-line " means described material in the pipeline or container that do not link to each other with reactor assembly.

In another embodiment, the present invention relates to the method for olefin polymerization in Gas-phase reactor, wherein at least two kinds of catalyzer and at least a activator add polymerization reactor in carrier fluid.In one preferred embodiment, before adding reactor, catalyzer and activator are mixed in carrier fluid.

In another embodiment, catalyzer is mixed in carrier fluid, add then with passage that reactor links to each other in, then activator is being added in the described passage with the identical or different position of described catalyzer.In another embodiment, catalyzer is mixed in carrier fluid, in described carrier fluid, add activator then.

In another embodiment, the carrier fluid that contains catalyzer and activator is placed on the device that is used for described carrier fluid is added reactor.In another embodiment, catalyzer and carrier fluid are added in the described device, then activator is added in the described device.

In another preferred embodiment, the described composition that comprises carrier fluid comprises the liquid stream that flows into or spray into described reactor.

In another preferred embodiment, at least a catalyzer, at least a activator and described carrier fluid are put into the device that is used for infeeding described reactor, other catalyzer adds described device after described first catalyzer and activator add described device.

Polymerization process

The solution feed of the invention described above catalyst composition, catalyst system, hybrid catalyst system, load type catalyst system or catalyst system is applicable to any polymerization process, comprises solution, gas phase or slurry process or its combination.Described polymerization process is preferably gas phase or slurry phase method, more preferably uses single reactor, most preferably single Gas-phase reactor.

In one embodiment, the present invention relates to make one or more that 2 to 30 carbon atoms, preferred 2 to 12 carbon atoms, the more preferably polymerization or the copolyreaction of the monomer polymerization of 2 to 8 carbon atoms are arranged.The present invention is specially adapted to make one or more olefinic monomer such as ethene, propylene, butene-1, amylene-1,4-methyl-amylene-1, hexene-1, octene-1, decylene-1,3-methyl-amylene-1,3,5, the copolyreaction of 5-trimethylammonium-hexene-1 and cycloolefin or its polymerization of mixtures.Other monomer can comprise vinyl monomer, diolefinic such as diene, polyenoid, norbornylene, norbornadiene monomer.The preferred multipolymer of producing ethene, wherein said comonomer are at least a have 4 to 15 carbon atoms, preferred 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, the alpha-olefins of 4 to 7 carbon atoms most preferably.In another embodiment, available the present invention makes among the WO98/37109 disclosed together with dibasic olefinic polymerization or copolymerization.

In another embodiment, make the comonomer polymerization different of ethene or propylene form terpolymer with at least two kinds.Preferred comonomer is that 4 to 10 carbon atoms, the more preferably mixture of the 'alpha '-olefin monomers of 4 to 8 carbon atoms are arranged, alternatively with at least a diene monomers combination.Preferred terpolymer comprises combinations such as ethylene/butylene-1/ hexene-1, ethylene/propene/butene-1, propylene/ethylene/hexene-1, ethylene/propene/norbornylene.

In one particularly preferred embodiment, the inventive method relates to ethene and at least a polymerization that the comonomer of 3 to 8 carbon atoms, preferred 4 to 7 carbon atoms is arranged.Especially, described comonomer is butene-1,4-methyl-amylene-1, hexene-1 and octene-1, most preferably is hexene-1 and/or butene-1.

Typically in gaseous polymerization, adopt circulation continuously, wherein in a reactor assembly round-robin part, circulating current (being also referred to as recycle stream or fluidizing medium) is heated by the heat of polymerization in the reactor.In described round-robin another part, from described circulation composition, remove this heat by the cooling system outside the reactor.Usually, in the gas fluidized bed method that is used for producing polymkeric substance, contain one or more monomeric air-flow continuously by under reaction conditions, there being the fluidized bed circulation of catalyzer.Give off gas stream from fluidized-bed, and the circulation Returning reactor.Simultaneously, from reactor, take out polymeric articles, add fresh monomer and substitute the polymeric monomer.(, all be incorporated herein for reference referring to for example US4543399,4588790,5028670,5317036,5352749,5405922,5436304,5453471,5462999,5616661 and 5668228.)

Reactor pressure can change to about 500psig (3448kPa) scope at about 10psig (69kPa) in the vapor phase process, preferably at about 100psig (690kPa) to about 400psig (2759kPa) scope, preferably at about 200psig (1379kPa) to about 400psig (2759kPa) scope, more preferably at about 250psig (1724kPa) extremely in about 350psig (2414kPa) scope.

Temperature of reactor can change to about 120 ℃ of scopes about 30 in the vapor phase process, preferably about 60 to about 115 ℃ scope, more preferably in about 75 to 110 ℃ scope, most preferably about 85 to about 110 ℃ scope.Change polymerization temperature and can be used as the means that change final polymeric articles performance.

The productive rate of catalyzer or catalyst system is influenced by the main monomer dividing potential drop.The molar percentage of preferred main monomer (ethene or propylene, optimal ethylene) is about 25 to 90% (moles), and described monomeric branch is pressed in about 75psia (517kPa) to the scope of about 300psia (2069kPa), and this is the representative condition of gaseous polymerization.In one embodiment, ethylene partial pressure is about 220 to 240psi (1517-1653kPa).In another embodiment, the mol ratio of hexene and ethene is 0.03:1 to 0.08:1 in the reactor.

In another embodiment, the reactor that is used for the present invention and the inventive method produces more than 500lbs polymkeric substance/hr (227kg/hr) to about 200000lbs/hr (90900kg/hr) or heteropolymer more, preferably more than 1000lbs/hr (455kg/hr), more preferably more than 10000lbs/hr (4540kg/hr), even more preferably more than 25000lbs/hr (11300kg/hr), also more preferably more than 35000lbs/hr (15900kg/hr), also more preferably more than 50000lbs/hr (22700kg/hr), most preferably more than 65000lbs/hr (29000kg/hr) to more than 100000lbs/hr (45500kg/hr).

Other vapor phase process that the inventive method comprised comprises those described in US5627242,5665818 and 5677375, EP-A-0794200, EP-A-0802202 and the EP-B-634421, all is incorporated herein for reference.

Slurry polymerization process is general to be adopted in about 1 the temperature of pressure and 0 to about 120 ℃ of scopes to about 50 normal atmosphere even the higher scope.In slurry polymerization, in ethene and comonomer and normally used hydrogen and catalyzer adding liquid polymerization diluent media wherein, form the suspension of solid particulate shaped polymer.Intermittently or continuously from reactor, take out the suspension that contains thinner, from polymkeric substance, isolate volatiles, after distillation, loop back reactor alternatively.Used liquid diluent typically is the paraffinic hydrocarbons of 3 to 7 carbon atoms, preferred branched paraffinic hydrocarbons in the described polymerisation medium.Used medium should be liquid under polymerizing condition, and relative inertness.When using propane medium, described process must and be operated more than the pressure in the critical temperature of reaction diluent.Preferred hexane or the Trimethylmethane medium of using.

In one embodiment, the preferred polymerization technique of the present invention is called the granule type polymerization or keeps temperature to be lower than the slurry process that polymkeric substance enters the temperature of solution.This technology is known in this field, for example is described among the US3248179, is incorporated herein for reference.Preferred temperature is in the scope of about 185 to about 230 ℉ (about 85-110 ℃) in the granule type polymerization.Two kinds of preferred slurry polymerization processes be adopt loop reactor those and adopt those of stirring reactor of a plurality of serial or parallel connections or its combination.The non-limitative example of slurry process comprises successive loops or stirring tank method.Other example of slurry process is described among the US4613484, is incorporated herein for reference.

In another embodiment, described slurry process carries out in loop reactor continuously.Described catalyzer is full of the loop slurry of growth polymerization composition granule in the isobutane diluent that contains monomer and comonomer with solution, suspension, emulsion, slurries in Trimethylmethane or free-pouring dry powder form injecting reactor loop regularly in the reactor loop.Can randomly add hydrogen as molecular weight regulator.Described reactor is maintained at about under the pressure and the temperature in about 140 to about 220 ℉ (about 60-104 ℃) scope of 525 to 625psig (3620-4309kPa), depends on the density polymer of wanting.Remove reaction heat by the loop wall, because most reactor is the double jacket form of tubes.Make described slurries leave reactor at regular intervals or continuously, the low pressure flash container, rotatory drier and the nitrogen purging tower that enter heating successively are to remove isobutane diluent and all unreacted monomer and comonomer.Then gained is not had the compounding of hydrocarbon powder and be used for various application.

In one embodiment, the reactor that is used for slurry process of the present invention can produce more than 2000lbs polymkeric substance/hr (907kg/hr), more preferably more than 5000lbs/hr (2268kg/hr), most preferably more than 10000lbs/hr (4540kg/hr).In another embodiment, the slurry-phase reactor that is used for the inventive method produces more than 15000lbs polymkeric substance/hr (6804kg/hr), preferably more than 25000lbs/hr (11340kg/hr) to about 100000lbs/hr (45500kg/hr).

In another embodiment of slurry process of the present invention, total reactor pressure at 400psig (2758kPa) to the scope of about 800psig (5516kPa), preferred 450psig (3103kPa) is to about 700psig (4827kPa), more preferably 500psig (3448kPa) is to about 650psig (4482kPa), and most preferably from about 525psig (3620kPa) is to 625psig (4309kPa).

In another embodiment of slurry process of the present invention, ethylene concentration is in the scope of about 1 to 10% (weight) in the liquid reactor medium, and preferred about 2 to about 7% (weight), and more preferably from about 2.5 to about 6% (weight), and most preferably from about 3 to about 6% (weight).

The present invention's one preferred method is not exist or be substantially free of method of operating, preferred slurries or vapor phase process under the situation of any scavenging agent such as triethyl aluminum, trimethyl aluminium, triisobutyl aluminium and tri-n-hexyl aluminum and diethylaluminum chloride, dibutyl zinc etc.This preferred method is described among WO96/08520 and the US5712352, is incorporated herein for reference.

In the present invention's one preferred embodiment, slurries metallizing thing and/or the activator of aluminium distearate in mineral oil adds reactor dividually or with described first and/or second metal complexes and/or with activator.About using the visible USSN 09/113261 of more information (1998.07.10 application) of aluminum stearate type additive, be incorporated herein for reference.

In another embodiment, if second kind of metallic compound of described catalyst system sequentially adds reactor with the metallic compound that contains the 15th family's element, then preferred described second metallic compound and/or first kind of metallic compound and/or second kind of metallic compound of activatory that promptly contains the 15th family's element of adding activatory of adding.

In another embodiment, the residence time of described catalyst composition between about 3 to about 6 hours, preferably about 3.5 and about 5 hours between.

In one embodiment, the mol ratio C of comonomer and ethene _x/ C ₂Between about 0.001 to 0.0100, more preferably between about 0.002 to 0.008, C wherein _xBe the amount of comonomer, C ₂Amount for ethene.

The melt index (with other character) of the polymkeric substance that can produce by density of hydrogen in the following controlled polymerization system changes:

1) amount of first catalyzer in the change paradigmatic system, and/or

2) amount of second catalyzer in the change paradigmatic system, and/or

3) in polymerization process, add hydrogen; And/or

4) change taking-up and/or the liquid of removing and/or the amount of gas from process; And/or

5) change the recovering liquid of returning polymerization process and/or amount and/or the composition that reclaims gas, described recovering liquid or recovery gas are to reclaim from the polymkeric substance that polymerization process is discharged; And/or

6) in polymerization process, use hydrogenation catalyst; And/or

7) change polymerization temperature; And/or

8) change ethylene partial pressure in the polymerization process; And/or

9) change the ratio of ethene and hexene in the polymerization process; And/or

10) change the ratio of activator and transition metal in the activation procedure.

Density of hydrogen is about 100 to 5000ppm in the reactor, preferred 200 to 2000ppm, and more preferably 250 to 1900ppm, and more preferably 300 to 1800ppm, more preferably 350 to 1700ppm, more preferably 400 to 1600ppm, and more preferably 500 to 1500ppm, and more preferably 500 to 1400ppm, more preferably 500 to 1200ppm, more preferably 600 to 1200ppm, and preferred 700 to 1100ppm, and more preferably 800 to 1000ppm.Weight-average molecular weight (the M of density of hydrogen and polymkeric substance in the reactor _w) be inversely proportional to.

Polymkeric substance of the present invention

The novel polymer of producing by the inventive method can be used for many kinds of products and final the application.Preferred described novel polymer comprises polyethylene and the bimodal polyethylene of producing by hybrid catalyst system of the present invention in single reactor.Except that bimodal polymers, with described hybrid catalyst system produce unimodal or multi-modal polymer also within the scope of the invention.

When the described metallic compound that contains the 15th family's element uses separately, produce high weight-average molecular weight Mw polymkeric substance (for example be higher than 100000, preferably be higher than 150000, preferably be higher than 200000, preferably be higher than 250000, more preferably be higher than 300000).When described second kind of metallic compound uses separately, produce low-molecular weight polymer (for example be lower than 80000, preferably be lower than 70000, preferably be lower than 60000, more preferably less than 50000, more preferably less than 40000, more preferably less than 30000, more preferably less than 20000 and be higher than 5000, more preferably less than 20000 and be higher than 10000).

The polyolefine that the present invention produces particularly polyethylene has 0.88-0.97g/cm ³The density of (measuring) by ASTM2839.But preferred production density is 0.910-0.965g/cm ³, more preferably 0.915-0.960g/cm ³, even more preferably 0.920-0.955g/cm ³Polyethylene.In some embodiment, preferred density is 0.915-0.940g/cm ³, in other embodiment, preferred density is 0.930-0.970g/cm ³

In one preferred embodiment, the polyolefine that is reclaimed typically have an appointment 0.01-1000dg/min or lower melt index I ₂(by ASTM D-1238, condition E is 190 ℃ of measurements).In one preferred embodiment, described polyolefine is Alathon or multipolymer.Be used for the preferred embodiment of some application as film, pipe and moulded product etc., preferred melt index is 10dg/min or lower.For some film and moulded product, preferred melt index is 1dg/min or lower.Preferred I ₂0.01 and 10dg/min between polyethylene.

In one preferred embodiment, the I of the polymkeric substance of producing ₂₁(by ASTM-D-1238-F 190 ℃ of measurements) is 0.1-10dg/min, preferred 0.2-7.5dg/min, preferred 2.0dg/min or lower, preferred 1.5dg/min or lower, preferred 1.2dg/min or lower, more preferably 0.5 and 1.0dg/min between, more preferably 0.6 and 0.8dg/min between.

In another embodiment, the melt flow index MIR (I of polymkeric substance of the present invention ₂₁/ I ₂) be 80 or higher, preferred 90 or higher, preferred 100 or higher, preferred 125 or higher.

In another embodiment, the I of described polymkeric substance ₂₁(by ASTM1238 condition F 190 ℃ of measurements) (being sometimes referred to as flow index) for 2.0dg/min or lower, preferred 1.5dg/min or lower, preferred 1.2dg/min or lower, more preferably 0.5 and 1.0dg/min between, more preferably 0.6 and 0.8dg/min between, I ₂₁/ I ₂Be 80 or higher, preferred 90 or higher, preferred 100 or higher, preferred 125 or higher, one or more of following character arranged in addition:

(a) Mw/Mn measures molecular weight (Mw and Mn) between 15 and 80, preferably between 20 and 60, preferably between 20 and 40 described in back embodiment part;

(b) Mw is 180000 or higher, preferred 200000 or higher, preferred 250000 or higher, preferred 300000 or higher;

(c) density (measuring by ASTM2839) is 0.94-0.970g/cm ³, preferred 0.945-0.965g/cm ³, preferred 0.950-0.960g/cm ³

(d) residual metal content is a 5.0ppm transition metal or lower, preferred 2.0ppm transition metal or lower, preferred 1.8ppm transition metal or lower, preferred 1.6ppm transition metal or lower, preferred 1.5ppm transition metal or lower, preferred 2.0ppm or lower group-4 metal, preferred 1.8ppm or lower group-4 metal, preferred 1.6ppm or lower group-4 metal, preferred 1.5ppm or lower group-4 metal, preferred 2.0ppm or lower zirconium, preferred 1.8ppm or lower zirconium, preferred 1.6ppm or lower zirconium, preferred 1.5ppm or lower zirconium (are measured by inductively coupled plasma emission spectrography (ICPAES) with respect to being purchased standard, wherein all organism are decomposed fully the sample heating, described solvent comprises nitric acid, if there is any carrier, then there is the another kind of acid (as the hydrofluoric acid of dissolved oxygen silicon carrier) of any carrier of dissolving;

(e) 35% (weight) or more, preferred 40% or how high weight-average molecular weight component (measuring) by the granularity exclusion chromatography.In one particularly preferred embodiment, described higher molecu lar weight component exist mark between 35 and 70% (weight), more preferably between 40 and 60% (weight).

In one preferred embodiment, prepare density 0.94 and 0.970g/cm with above-mentioned catalyst composition ³Between (measuring) and I by ASTM D 2839 ₂Be 0.5g/10min or lower polyethylene.

In another embodiment, prepare I with above-mentioned catalyst composition ₂₁Be lower than 10 and density about 0.940 and 0.950g/cm ³Or I ₂₁Be lower than 20 and the about 0.945g/cm of density ³Or lower polyethylene.

In another embodiment, polymkeric substance of the present invention is made pipe by means known in the art.For pipe applications, the I of polymkeric substance of the present invention ₂₁For about 2 to about 10dg/min, preferred about 2 to about 8dg/min.In another embodiment, pipe of the present invention satisfies the ISO quality authentication.

In another embodiment, be manufactured on catalyst composition of the present invention to use water as under 20 ℃ the envrionment temperature and (measure isotropy (circumferentially) stress) under closed test medium and water or air the situation and can stand the polyethylene tube at least 50 years by ISOTR 9080 as outside atmosphere.

In another embodiment, the notch tension test of described polymkeric substance (anti-crack expansibility) at a slow speed result under 3.0MPa greater than 150 hours, preferably under 3.0MPa greater than 500 hours, more preferably under 3.0MPa greater than 600 hours (measuring) by ASTM-F1473.

In another embodiment, with the S-4T of catalyst composition preparation of the present invention to the prediction of 110mm pipe _cBe lower than-5 ℃, preferably be lower than-15 ℃, more preferably less than the polyethylene tube of-40 ℃ (ISO DIS13477/ASTM F1589).

In another embodiment, the rate of extrusion of described polymkeric substance greater than about 17 lbs/hr/in die head girths, be preferably greater than about 20 lbs/hr/in die head girths, more preferably greater than about 22lbs/hr/in die head girth.

Polyolefine of the present invention can be made into film, moulded product (comprising pipe), sheet material, electric wire coating etc.Described film can comprise by any conventional art known in the art extrude, coextrusion, lamination, blowing and curtain coating make.Can obtain described film in the single shaft direction or in two mutually perpendicular directions of membrane plane with identical or different degree orientation then by flat film or tubular embrane method.Can be orientated to same degree at both direction, also can be orientated in various degree.The special preferred method that described polymkeric substance is made film is included on blowing or the casting films production line to be extruded or coextrusion.

In another embodiment, polymkeric substance of the present invention is made film by means known in the art.For film is used, the I of polymkeric substance of the present invention ₂₁For about 2 to about 50dg/min, preferred about 2 to about 30dg/min, and more preferably from about 2 to about 20dg/min, also more preferably from about 5 to about 15dg/min, also more preferably from about 5 to about 10dg/min.

In another embodiment, the MD of the .5mil of described polymkeric substance (13 μ) film tear about 5 and 25g/mil between, preferably about 15 and 25g/mil between, more preferably about 20 and 25g/mil between.

The film of being produced can also comprise additive such as slip(ping)agent, anti, antioxidant, pigment, filler, antifogging agent, UV stablizer, static inhibitor, polymer processing aids, neutralizing agent, lubricant, tensio-active agent, pigment, dyestuff and nucleator.Preferred additives comprises silicon-dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, lime carbonate, metallic stearate, calcium stearate, Zinic stearas, talcum, BaSO ₄, diatomite, wax, carbon black, flame-retardant additive, low-molecular-weight resin, hydrocarbon resin, granulated glass sphere etc.Described additive can typical significant quantity well known in the art exist, as 0.001 to 10% (weight).

In another embodiment, for example blowing and injection stretching molding are made moulded product to polymkeric substance of the present invention by means known in the art.For molding is used, the I of polymkeric substance of the present invention ₂₁For about 20 to about 50dg/min, preferred about 35 to about 45dg/min.

In another embodiment, produce ash oontent be lower than 100ppm, more preferably less than 75ppm even more preferably less than the polymkeric substance of the present invention of 50ppm (comprise above-mentioned those).In another embodiment, described ash content comprises by inductively coupled plasma/atomic emission spectrometry well known in the art (ICPAES) measures negligible very a spot of titanium.

In another embodiment, polymkeric substance of the present invention comprises can be by the containing n-donor ligand of high resolution mass spectrometry well known in the art (HRMS) detection.

Embodiment

For understanding the present invention's (comprising its representative advantages) better, provide following examples.

Definition:

Mn and Mw measure on the Waters150 that is furnished with differential refractive index detector ℃ of GPC instrument by gel permeation chromatography.Calibrate described GPC post by testing a series of molecular weight standard samples, with the Mark Houwink coefficient calculations molecular weight of described polymkeric substance.

MWD＝Mw/Mn

Density is pressed ASTM D 1505 and is measured.

The method that CDBI (forming the Tile Width index) presses among the WO93/03093 (1993.02.18 is open) is measured, and disregards but molecular weight is lower than the part of 10 000Mn.

Melt index (MI) I ₂Press ASTM D-1238 condition E 190 ℃ of measurements.

I ₂₁Press ASTM D-1238 condition F 190 ℃ of measurements.

Melt index is the I that measures by ASTM D-1238 than (MIR) ₂₁With I ₂The ratio.

The % of comonomer (weight) measures by proton N MR.

Dart Impact (dart impact strength) presses ASTM D 1709 and measures.

MD and TD Elmendorf Tear (elmendorf is torn) press ASTM D 1922 and measure.

MD and TD 1% secant modulus are pressed ASTM D 882 and are measured.

MD and TD tensile strength and ultimate tensile strength are pressed ASTM D 882 and are measured.

MD and TD elongation and elongation limit are pressed ASTM D 412 and are measured.

MD and TD modulus are pressed ASTM 882-91 and are measured.

Mist degree is pressed ASTM 1003-95 condition A and is measured.

45 ° of gloss are pressed ASTM D 2457 and are measured.

BUR is a blow-up ratio.26 in.Dart Impact (26 inches dart impact strengths) press ASTM D 1709 method A and measure.

ESCORENE ^TMLL3002.32 is available from Exxon Chemical Company inHouston, linear low density ethene-hexene copolymer of in single Gas-phase reactor, producing with Ziegler-natta catalyst of Texas, and density is 0.918g/cc, I ₂Be 2dg/min, CDBI (forming the Tile Width index) is less than 65.

EXCEED ^TMECD 125 is available from Exxon Chemical Company in Houston, linear low density ethene-hexene copolymer of in single Gas-phase reactor, producing with metalloscene catalyst of Texas, and density is about 0.91g/cc, MI is 1.5g/10min.

ESCORENE ^TMLL3001.63 is available from Exxon Chemicai Company inHouston, linear low density ethene-hexene copolymer of in single Gas-phase reactor, producing with Ziegler-natta catalyst of Texas, and density is 0.918g/cc, MI is 1.0g/10min.

EXCEED ^TM350D60 is available from Exxon Chemical Company in Houston, linear low density ethene-hexene copolymer of in single Gas-phase reactor, producing with metalloscene catalyst of Texas, and density is 0.918g/cc, MI is 1.0g/10min.

" PPH " be the pound/little, the time." mPPH " be milli pound/little, the time." ppmw " is per 1,000,000 parts parts by weight.MD is that vertically TD is horizontal.

Embodiment among following examples part I uses and comprises the metal catalyst that contains the 15th family's element and the hybrid catalyst system of big ligand metal cyclopentadienyl catalyst.

Embodiment part I. comprises that the metal catalyst and the big ligand metal that contain the 15th family's element are luxuriant The hybrid catalyst system of catalyzer

The preparation of three PIVALIC ACID CRUDE (25) indenyl zirconiums

Three PIVALIC ACID CRUDE (25) indenyl zirconiums (a kind of big ligand metal cyclopentadinyl compound is also represented by formula VI) can prepare by carrying out following total reaction:

(1)Zr(NEt ₂) ₄+IndH→IndZr(NEt ₂) ₃+Et ₂NH

(2)IndZr(NEt ₂) ₃+3(CH ₃) ₃CCO ₂H→IndZr[O ₂CC(CH ₃)] ₃+Et ₂NH

Ind=indenyl wherein, Et is an ethyl.

[(2,4,6-Me ₃C ₆H ₂) NHCH ₂CH ₂] ₂The preparation of NH part (ligand i)

The magnetic stirring bar of in single handle Schlenk flask of one 2 liters, packing into, under the nitrogen of dry anaerobic, add diethylenetriamine (23.450g, 0.227mol), 2-bromo-1,3, the 5-trimethylbenzene (90.51g, 0.455mol), three (dibenzalacetones), two palladiums (1.041g, 1.14mmol), racemize-2,2,-two (diphenyl phosphine)-1,1 ,-dinaphthalene (racemize BINAP) (2.123g, 3.41mmol), sodium tert-butoxide (65.535g, 0.682mol) and toluene (800ml).Stirred reaction mixture also is heated to 100 ℃.After 18 hours, reaction finishes, and judges by proton N MR spectrography.Remaining operation all can carry out in air.Remove all solvents under vacuum, resistates is dissolved in diethyl ether (1L).With described ether washing (washing 3 times), use the saturated NaCl aqueous solution (180g is in 500ml) washing then, through sal epsom (30g) drying with 250ml.Remove ether in a vacuum and produce reddish oil, under vacuum in 70 ℃ of dryings 12 hours (output: 71.10g, 92%). ¹H?NMR(C ₆D ₆)δ?6.83(s，4)，3.39(brs，2)，2.86(t，4)，2.49(t，4)，2.27(s，12)，2.21(s，6)，0.68(brs，1)。

The preparation of catalyst A (being used for this embodiment part I)

The toluene solution of 1.5wt% catalyzer

Annotate: following institute all carries out in glove box in steps.

1. taking by weighing the 100g pure toluene adds in 1 liter of Erlenmeyer flask of the stirring rod of being furnished with the teflon of being coated with.

2. add 7.28g tetrabenzyl zirconium.

3. solution is placed on the agitator, stirred 5 minutes.All solids is all in the pass into solution.

4. add the ligand i that 5.42g prepares previously.

5. add the 551g pure toluene again, mixture was stirred 15 minutes.Remaining solid not in the solution.

6. catalyst solution is poured in 1 liter of Whitey test specimen tube that clean purging crosses, labelled, from glove box, take out, be placed on the conservation zone and be used for operation.

Compound I [(2,4,6-Me ₃C ₆H ₂) NCH ₂CH ₂] ₂NH}Zr (CH ₂Ph) ₂Preparation

The magnetic stirring bar of in a 500ml round-bottomed flask, packing into, under the nitrogen of dry anaerobic, add tetrabenzyl zirconium (Boulder Scientific) (41.729g, 91.56mmol) and 300ml toluene.Under agitation added above-mentioned solid ligand I (32.773g, 96.52mmol) (compound precipitation of wanting) through 1 minute.Make slurry volume reduce to 100ml, under agitation add the 300ml pentane.Filter and collect the yellowish-orange solid product, under vacuum dry (44.811g, 80% productive rate). ¹H?NMR(C ₆D ₆)δ?7.22-6.81(m，12)，5.90(d，2)，3.38(m，2)，3.11(m，2)，3.01(m，1)，2.49(m，4)，2.43(s，6)，2.41(s，6)，2.18(s，6)，1.89(s，2)，0.96(s，2)。

The preparation of catalyst B (for this embodiment part I)

The hexane solution of 1wt% catalyst B

Following institute all carries out in glove box in steps.

1. 1 liter of pure hexane is moved in 1 liter of Erlenmeyer flask of the stirring rod of being furnished with the teflon of being coated with.

2. add 6.67g three PIVALIC ACID CRUDE (25) indenyl zirconium dry powder.

3. solution is placed on the magnetic stirring apparatus, stirred 15 minutes.All solids is all in the pass into solution.

4. solution is poured in 1 liter of Whitey test specimen tube that clean purging crosses, labelled, from glove box, take out, be placed on the conservation zone until being used for operation.

Embodiment part I-Comparative Examples 1:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 40lbs/hr (18.1kg/hr), and hexene infeeds reactor with the speed of about 0.6lbs/hr (0.27kg/hr), and hydrogen infeeds reactor with the speed of 5mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 27PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1900PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, as describing in detail among the US5 693 727, is incorporated herein for reference.) the taper catalyzer syrup filling tip of aperture 0.041in. (0.10cm) is arranged in the aeration gas flow.The toluene solution of 1wt% catalyst A and promotor (MMAO-3A, 1wt% aluminium) on-line mixing before entering fluidized-bed by described syrup filling tip.(MMAO-3A is the n-heptane solution of modified methylaluminoxane, available from Akzo Chemicals, and Inc., trade(brand)name Modified Methylalumoxane type 3A.) to make the Al:Zr mol ratio be 400:1 for the relative quantity of control MMAO and catalyzer.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 0.28dg/min (I ₂₁) and the unimodal polymerisation thing of 0.935g/cc (density) character.Calculate residual zirconium 1.63ppmw based on the reactor mass balance.

Embodiment part I-Comparative Examples 2:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 80 ℃ and 320psig (2.2MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 37lbs/hr (19.8kg/hr), and hexene infeeds reactor with the speed of about 0.4lbs/hr (0.18kg/hr), and hydrogen infeeds reactor with the speed of 12mPPH.Infeed ethene and make maintenance 180psi (1.2MPa) ethylene partial pressure in the reactor.Productivity is about 25PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1030PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa.) the taper catalyzer syrup filling tip of aperture 0.055in. (0.14cm) is arranged in the aeration gas flow.The hexane solution of 1wt% catalyst B was mixed about 15 minutes in 3/16in (0.48cm) stainless steel tube with 0.2lb/hr (0.09kg/hr) hexene.Make about 40 minutes of the mixture of described catalyst B and hexene and promotor (MMAO-3A, 1wt% aluminium) on-line mixing.Except that described solution, also add iso-pentane and nitrogen with control size.Total system enters fluidized-bed through syrup filling tip.It is 300:1 that the ratio of control MMAO and catalyzer makes the Al:Zr mol ratio.Produce bimodal polymers, its melt index is 797g/10min.Density is 0.9678g/cc.Calculate residual zirconium 0.7ppmw based on the reactor mass balance.Carry out SEC and analyze, distribute with 4 kinds of powder (floury) and remove flatung, the results are shown in the Table I.

Embodiment part I-embodiment 3:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 80 ℃ and 320psig (2.2MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 53lbs/hr (24kg/hr), and hexene infeeds reactor with the speed of about 0.5lbs/hr (0.22kg/hr), and hydrogen infeeds reactor with the speed of 9mPPH.Infeed ethene and make maintenance 220psi (1.52MPa) ethylene partial pressure in the reactor.Productivity is about 25PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 990PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa.) the taper catalyzer syrup filling tip of aperture 0.055in. (0.12cm) is arranged in the aeration gas flow.The hexane solution of 1wt% catalyst B was mixed about 15 minutes in 3/16in (0.48cm) stainless steel tube with 0.2lb/hr (0.09kg/hr) hexene.The mixture and the promotor (MMAO-3A, 1wt% aluminium) of described catalyst B and hexene were mixed about 20-25 minute in pipeline.In another activation stainless steel tube, make the toluene solution of 1wt% catalyst A activate about 50-55 minute with promotor (MMAO-3A, 1wt% aluminium).Two kinds of independent activatory solution were mixed in a process pipe about 4 minutes.The amount of catalyst A is about 40-45% (mole) of total solution feed.Except that described solution, also add iso-pentane and nitrogen with control size.Total system enters fluidized-bed through syrup filling tip.It is 300:1 that the ratio of control MMAO and catalyzer makes the Al:Zr mol ratio.Produce bimodal polymers, its melt index is 0.045g/10min, and flow index is 7.48g/10min.Density is 0.9496g/cc.Calculate residual zirconium 1.7ppmw based on the reactor mass balance.Carry out SEC and analyze, remove flatung, the results are shown in the Table I with the heavy powder distribution of 7-8.

Embodiment part I-embodiment 4:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 320psig (2.2MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 50lbs/hr (22.7kg/hr), and some hexenes infeed reactor with the speed of about 0.7lbs/hr (0.32kg/hr), and hydrogen infeeds reactor with the speed of 11mPPH.Infeed ethene and make maintenance 220psi (1.52MPa) ethylene partial pressure in the reactor.Productivity is about 29PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 970PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa.) the taper catalyzer syrup filling tip of aperture 0.055in. (0.14cm) is arranged in the aeration gas flow.The hexane solution of 1wt% catalyst B was mixed about 15 minutes in 3/16in (0.48cm) stainless steel tube with 0.2 lb/hr (0.09kg/hr) hexene.The mixture and the promotor (MMAO-3A, 1wt% aluminium) of described catalyst B and hexene were mixed about 20-25 minute in pipeline.In another activation stainless steel tube, make the toluene solution of 1wt% catalyst A activate about 50-55 minute with promotor (MMAO-3A, 1wt% aluminium).Two kinds of independent activatory solution were mixed in a process pipe about 4 minutes.The amount of catalyst A is about 40-45% (mole) of total solution feed.Except that described solution, also add iso-pentane and nitrogen with control size.Total system enters fluidized-bed through syrup filling tip.It is 300:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Produce bimodal polymers, its melt index is 0.054g/10min, and flow index is 7.94g/10min.Density is 0.948g/cc.Calculate residual zirconium 1.1ppmw based on the reactor mass balance.Carry out SEC and analyze, remove flatung, the results are shown in the Table I with the heavy powder distribution of 7-8.

Embodiment part I-embodiment 5:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 320psig (2.2MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 60lbs/hr (27.2kg/hr), and hexene infeeds reactor with the speed of about 0.8lbs/hr (0.36kg/hr), and hydrogen infeeds reactor with the speed of 13mPPH.Infeed ethene and make maintenance 220psi (1.52MPa) ethylene partial pressure in the reactor.Productivity is about 34PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 960PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa.) the taper catalyzer syrup filling tip of aperture 0.055in. (0.14cm) is arranged in the aeration gas flow.The hexane solution of 1wt% catalyst B was mixed about 15 minutes in 3/16in (0.48cm) stainless steel tube with 0.2lb/hr (0.09kg/hr) hexene.The mixture and the promotor (MMAO-3A, 1wt% aluminium) of described catalyst B and hexene were mixed about 20-25 minute in pipeline.In another activation stainless steel tube, make the toluene solution of 1wt% catalyst A activate about 50-55 minute with promotor (MMAO-3A, 1wt% aluminium).Two kinds of independent activatory solution were mixed in a process pipe about 4 minutes.The amount of catalyst A is about 40-45% (mole) of total solution feed.Except that described solution, also add iso-pentane and nitrogen with control size.Total system enters fluidized-bed through syrup filling tip.It is 300:1 that the ratio of control MMAO and catalyzer makes the Al:Zr mol ratio.Produce bimodal polymers, its melt index is 0.077g/10min, and flow index is 12.7g/10min.Density is 0.9487g/cc.Calculate residual zirconium 0.9ppmw based on the reactor mass balance.Carry out SEC and analyze, remove flatung, the results are shown in the Table I with the heavy powder distribution of 7-8.

Embodiment part I-embodiment 6:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 320psig (2.2MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 60lbs/hr (27.2kg/hr), and hexene infeeds reactor with the speed of about 0.8lbs/hr (0.36kg/hr), and hydrogen infeeds reactor with the speed of 13mPPH.Infeed ethene and make maintenance 220psi (1.52MPa) ethylene partial pressure in the reactor.Productivity is about 34PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1100PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa.) the taper catalyzer syrup filling tip of aperture 0.055in. (0.14cm) is arranged in the aeration gas flow.The hexane solution of 1wt% catalyst B was mixed about 15 minutes in 3/16in (0.48cm) stainless steel tube with 0.2lb/hr (0.09kg/hr) hexene.The mixture and the promotor (MMAO-3A, 1wt% aluminium) of described catalyst B and hexene were mixed about 10-15 minute in pipeline.The toluene solution of 1wt% catalyst A is added in the described activatory catalyst B solution, before spraying into reactor, mixed about 5 minutes.The amount of catalyst A is about 40-45% (mole) of total solution feed.Except that described solution, also add iso-pentane and nitrogen with control size.Total system enters fluidized-bed through syrup filling tip.It is 300:1 that the ratio of control MMAO and catalyzer makes final Al:Zr mol ratio.Produce bimodal polymers, its melt index is 0.136g/10min, and flow index is 38.1g/10min.Density is 0.9488g/cc.Calculate residual zirconium 0.5ppmw based on the reactor mass balance.Carry out SEC and analyze, remove flatung, the results are shown in the Table I with the heavy powder distribution of 7-8.

Embodiment part I-embodiment 7:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 42lbs/hr (19.1kg/hr), and hexene infeeds reactor with the speed of about 0.8lbs/hr (0.36kg/hr), and hydrogen infeeds reactor with the speed of 13mPPH.Infeed ethene and make maintenance 220psi (1.52MPa) ethylene partial pressure in the reactor.Productivity is about 32PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 2010PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa.) the taper catalyzer syrup filling tip of aperture 0.055in. (0.14cm) is arranged in the aeration gas flow.The hexane solution of 0.25wt% catalyst B is mixed in 3/16in (0.48cm) stainless steel tube with 0.1lb/hr (0.05kg/hr) hexene.The mixture and the promotor (MMAO-3A, 1wt% aluminium) of described catalyst B and hexene were mixed about 15 minutes in pipeline.The toluene solution of 0.5wt% catalyst A is added in the described activatory catalyst B solution, before spraying into reactor, mixed about 15 minutes.The amount of catalyst A is about 65-70% (mole) of total solution feed.Except that described solution, also add iso-pentane and nitrogen with control size.Total system enters fluidized-bed through syrup filling tip.It is 500:1 that the ratio of control MMAO and catalyzer makes final Al:Zr mol ratio.Produce bimodal polymers, its melt index is 0.06g/10min, and flow index is 6.26g/10min.Density is 0.9501g/cc.Calculate residual zirconium 0.65ppmw based on the reactor mass balance.Carry out SEC and analyze, remove flatung, the results are shown in the Table I with the heavy powder distribution of 7-8.

Table 1

Embodiment part I-Comparative Examples 1 and 2 provides the testing data of single component catalyst system.Embodiment 3 and 4 is illustrated in Temperature Influence under reactor condition and the essentially identical situation of catalyst charge system.Notice that Mw/Mn is lower under comparatively high temps, MFR too.The influence of embodiment 5 and 6 contrasts activation method under reactor condition and the essentially identical situation of catalyst charge system.Notice that among the embodiment 6, the gross activity of catalyzer is better.But the amount of the high molecular weight material that produces is less.The ability of embodiment 6 and 7 proofs turnout of control high molecular weight material under essentially identical reactor condition.Embodiment 7 infeeds higher percentile catalyst A, thereby the turnout of higher Mw material is higher.

Embodiment part I-embodiment 8:

Make embodiment 4 produces above the 350lbs (159kg) polyethylene (being called polymer A) on Werner-Fleiderer ZSK-30 twin screw extruder with 1000ppm Irganox ^TM1076 and 1500ppm IrgafoS ^TM1068 compoundings under 220 ℃ melt temperature form pelletizing.Then described pelletizing is blow molded into the film of 0.5mil (13 μ m) on Alpine extrusion blow film line.Extrusion condition is: three ones of die head-160mm (triplex), die gap 1.5mm, 400 ℃ of die head temperatures, flat width 48in (122cm), target melt temperature-410 ℉ (210 ℃), rate of extrusion-310lb/hr (144kg/hr), 420lb/hr (191kg/hr) and 460lb/hr (209kg/hr).Test ESCORENE under the same conditions ^TMHD7755.10 (Exxon Chemical Company, Houston, traditional serial reaction device product of Texas) as a comparison.All films were all pressed 23 ℃, 50% humidity conditioning 40 hours.Data are shown among the Table I A.

Table I A

	Polymer A	HD7755.10	Polymer A	HD7755.10	Polymer A	HD7755.10
							Speed lb/hr/ (kg/hr)	317(144)	317(144)	421(191)	421(191)	460(209)	460(209)
Thickness	0.524mil/13μm	0.502mil/13μm	0.532mil/14μm	0.519mil/13μm	0.543mil/14μm	0.528mil/13μm
							Density g/cc	0.9489	0.949	0.9502	0.949	0.9468	0.9489
26 " (66cm) Luo Biao @1 days	355g	308g	327g	325g	Nm	nm
							26 ＂ (66cm) Luo Biao @7 days	351g	308g	314g	344g	301g	360g
MD tears g/mil (g/ μ)	22(0.87)	16(0.63)	25(0.98)	15(0.59)	22(0.87)	15(0.59)
							TD tears g/mil (g/ μ)	97(3.82)	102(4.02)	77(3.03)	84(3.31)	100(3.94)	81(3.19)
1% secant MD, psi (MPa)	161,000(1110)?	200,200(1380)?	159,000(1096)?	183,800(1267)?	156,200(1077)?	178,700(1232)?
							1% secant TD, psi (MPa)	184.500(1272)?	212,500(1465)?	163,500(1127)?	206,600(1425)?	161,400(1113)?	212,500(1465)?
MDUTStr.Psi(MPa)	14445(100)	14347(99)?	12574(87)?	15110(104)	12934(89)?	15609(108)
							TDUTStr.Psi(MPa)	13369(92)?	12124(84)?	10785(74)?	12278(85)?	11727(81)?	11482(79)?
UE1ong.％	285	293	246	296	253	299
							U.E1on.％	317	393	305	377	340	377
Mist degree %	59.6	64.0	57.8	62.0	56.9	60.9
							45 ° of gloss	13.6	10.8	13.4	12.0	14.9	11.9

MD=is vertical, and TD=is horizontal, UT Str=ultimate tensile strength, U.Elong=elongation limit

ESCORENE HD7755.10 is available from Exxon Chemical Company, Houston, the polyethylene polymer of Texas, I ₂₁Be 7.5, MIR is 125, and Mw is 180 000, and density is 0.95g/cc, produces with two reactor system.

Embodiment part I-embodiment 9:

Make several barrels of granular samples (is to produce by above-mentioned polymerization process for 2.3 times in the mol ratio of catalyst A/catalyst B) and 1000ppm Irganox ^TM1076 and 1500ppm Irgafos ^TM1068 and 1500ppm calcium stearate bucket mix.Granular resin after this barrel mixed is 21/2 " (6.35cm) on the Prodex compounding production line in 400 ℉ (204 ℃) granulation down.The pelletizing that makes is extruded into film on the 50mm Alpine blown film production line of the 100mm annular die forcing machine of being furnished with the single screw rod of 50mm (L/D is than being 18:1), die gap 1mm.Extrusion condition is as follows: die head temperature 400 ℉ (204 ℃), discharging speed-100lb/hr (46kg/hr).Typical design temperature distributes: and 1/ barrel of 2/ Die-head connecting sleeve/bottom of bucket connects in the middle of cover/vertical junction cover/die head bottom/die head/and the die head top is respectively 380 ℉/400 ℉/400 ℉/400 ℉/400 ℉/400 ℉/410 ℉/410 ℉ (193 ℃/204 ℃/204 ℃/204 ℃/204 ℃/204 ℃/210 ℃/210 ℃).Is to extrude the film sample that produces 1.0mil (25 μ m) with the linear speed of 92fpm (48cm/sec) 4.0 times with the blank sample in blow-up ratio (BUR), extrudes the film sample that produces 0.5mil (13 μ m) with the linear speed of 184fpm (94cm/sec).The film bubble all shows fabulous stability under two kinds of situations, and typical " necking down " wine glass-shaped is arranged.1.0mil the FLH (frost line height) of the blown film of (25 μ m) and 0.5mil (12.5 μ m) film bubble remains on 36in (91.4cm) and 40in (101.6cm) respectively.Cross-head pressure and a little higher than ESCORENE of engine load under the identical situation of extrusion condition ^TMHD7755.10 (traditional serial reaction device product of Exxon Chemical Company in Mt Belvue Texas).The character of gained film is shown among the Table I B.The all conditionings 40 hours under 23 ℃, 50% humidity of all film samples.0.5mil the dart impact strength of (12.5 μ m) film is 380g, is higher than ESCORENE ^TMHD7755.10 (its dart impact strength is 330g).

Table I B

MD=is vertical, and TD=is horizontal.

Embodiment part I-embodiment 10:

Press the method for embodiment 9, make several barrels of granular samples (mol ratio of catalyst A/catalyst B is the polymkeric substance C that produces by above-mentioned polymerization process for 0.732 time and is the polymkeric substance D that produce by above-mentioned polymerization process for 2.6 times in the mol ratio of catalyst A/catalyst B) and 1000ppmIrganox ^TM1076,1500ppm calcium stearate and 1500ppm Irgafos ^TM1068 barrels are mixed, then granulation and extruding as described in example 9 above.The all conditionings 40 hours under 23 ℃, 50% humidity of all film samples.The dart impact strength of 0.5mil (the 12.5 μ m) film of being made by polymkeric substance C and polymkeric substance D is 380g, is higher than ESCORENE ^TMHD7755.10 (its dart impact strength is 330g).These data are shown among the Table I C.

Table I C

Table I C

The Alpine production line, 2 " screw rod, 4in (10.2cm) die head, 40mil (1016 μ m) die gap, 410 ℉ (210 ℃) die head design temperature.

Except that above embodiment, other variation during with catalyst system polymerization described herein comprises:

1. make Compound I be dissolved in solvent (preferred toluene) and form the solution that requires wt%, be used in combination with other catalyst system then.

2. catalyst A is used with 0.50wt% toluene solution form, catalyst B is used with 0.25wt% hexane solution form, the mol ratio of B and A was about 0.7 when two kinds of independent activation of catalyzer mixed then, and the mol ratio of B and A is 2.2 to 1.5 when perhaps making the A activation add B (sequential activation) then.

3. rising or reduction temperature of reaction make Mw/Mn narrow down respectively or broaden.

4. the change residence time influences product property.Change and have remarkably influenced when big.As if the residence time of 1 to 5 (preferred 4) hour produce good product property.

5. described catalyzer sprays into reactor by this way to produce poor pars granulosa.Make the 50000lb/hr circulating current can produce poor pars granulosa by the 6in pipe.Available nitrogen atomization gas makes the catalyzer atomizing by nozzle.

6. iso-pentane, hexane or the n-heptane solution form that activator (preferred MMAO 3A) can 7wt% aluminium is to be enough to making Al/Zr than the feeding rate use that reaches 100 to 300.

7. make catalyst A and MMAO 3A on-line mixing, online then adding catalyst B adds reactor with mixture again.

8. make catalyst A and MMAO 3A on-line mixing, make catalyst B and MMAO 3A on-line mixing, make two kinds of activatory catalyzer on-line mixing then, add reactor again.

Embodiment among following examples part II uses the catalyst system of the metal catalyst that contains the 15th family's element that includes the benzyl ionic group.

Embodiment part II. includes the metal catalytic that contains the 15th family's element of benzyl leavings group The catalyst system of agent

As among the embodiment part I of front the preparation [(2,4,6-Me ₃C ₆H ₂) NHCH ₂CH ₂] ₂Or (NH part) and [(2,4,6-Me ₃C ₆H ₂) NCH ₂CH ₂] ₂NH}Zr (CH ₂Ph) ₂Or (Zr-HN ₃).

[(2,4,6-Me ₃C ₆H ₂) NCH ₂CH ₂] ₂NH}ZrCl ₂Or (ZrCl ₂-HN ₃) preparation

In the 250ml round-bottomed flask, make 5.480g Zr (NMe ₂) ₄(20.48mmol) be dissolved in the 50ml pentane.Add 6.656g[(2,4,6-Me with pentane solution (50ml) form ₃C ₆H ₂) NHCH ₂CH ₂] ₂NH (20.48mmol) was with solution stirring 2 hours.By proton N MR identify described mixed amide [(2,4,6-Me ₃C ₆H ₂) NCH ₂CH ₂] ₂NH}Zr (NMe ₂) ₂But do not separate. ¹H?NMR(C ₆D ₆)δ6.94(m，4)，3.33(m，2)，3.05(s，6)，3.00(m，2)，2.59(m，4)，2.45(s，6)，2.43(s，6)，2.27(s，6)，2.20(s，6)，1.80(m，1)。Under vacuum, remove and desolvate.Make resistates be dissolved in toluene, with 6.0g ClSiMe ₃(55mmol) once add.With solution stirring 24 hours.Under vacuum, remove and desolvate, make solid suspension in pentane.Solid collected by filtration is with pentane washing (5.528g, 54% productive rate).By proton N MR identify described dichloride [(2,4,6-Me ₃C ₆H ₂) NCH ₂CH ₂] ₂NH}ZrCl ₂ ¹H NMR (C ₆D ₆) δ 6.88 (s, 2), 6.81 (s, 2), 3.32 (m, 2), 2.86 (m, 2), 2.49 (s, 6), 2.47 (m, 4), 2.39 (s, 6), 2.12 (s, 6), NH is not obvious.

The preparation of catalyst A (for this embodiment part II)

(6.836g 30wt% toluene solution, available from Albemarle Corporation, Baton Rouge Louisiana) with in the 7.285g toluene adds 0.145g ZrCl to 2.051g MAO in the 100ml round-bottomed flask ₂-HN ₃With described solution stirring 15 minutes.Add the 5.070g silicon oxide (Davison 948,600 ℃ baked, available from W.R.Grace, DavisonDivision, Baltimore Maryland), mixes then.With mixture dried overnight under vacuum, obtain the 7.011g finished catalyst, zirconium load is 0.36wt%, Al/Zr is than being 122:1.

The preparation of catalyst B (for this embodiment part II)

(2.670g 30wt% toluene solution, available from Albemarle Corporat ion, Baton Rouge Louisiana) with in the 4.679g toluene adds 0.070g Zr-HN to 0.801g MAO in the 100ml round-bottomed flask ₃With described solution stirring 15 minutes.Add the 2.130g silicon oxide (DaviSon 948,600 ℃ baked, available from W.R.Grace, DavisonDivision, Baltimore Maryland), mixes then.With mixture dried overnight under vacuum, obtain the 2.899g finished catalyst, zirconium load is 0.35wt%, Al/Zr is than being 120:1.

The slurry phase vinyl polymerization of embodiment part II-Comparative Examples 1 usefulness catalyst A

Carry out slurry phase polymerisation at 1 liter of autoclave reactor being furnished with mechanical stirrer, being used for outside water jacket, the barrier film inlet and the vent line of controlled temperature and supplying with drying nitrogen and ethene regularly.Make the reactor drying, 160 ℃ of degassings down.Add Trimethylmethane (400ml) as thinner with gastight syringe, the hexane solution that adds 0.7ml 25wt% trioctylaluminum is as scavenging agent.Reactor is heated to 90 ℃.Under ethylene pressure, add 0.200g finished catalyst A, pressurize to reactor with 143psi (986kPa) ethene.Reactor is remained under the situation of 90 ℃ and 143psi (986kPa), and described polymerization continues 40 minutes.By rapid cooling and emptying stopped reaction.Obtain 10.5g polyethylene (flow index (FI)=not flows, activity=209g polyethylene/mmol catalyzer atmh).

Implement the slurry phase vinyl polymerization of the II-of falling part embodiment 2 usefulness catalyst B

Carry out slurry phase polymerisation at 1 liter of autoclave reactor being furnished with mechanical stirrer, being used for outside water jacket, the barrier film inlet and the vent line of controlled temperature and supplying with drying nitrogen and ethene regularly.Make the reactor drying, 160 ℃ of degassings down.Add Trimethylmethane (400ml) as thinner with gastight syringe, the hexane solution that adds 0.7ml 25wt% trioctylaluminum is as scavenging agent.Reactor is heated to 90 ℃.Under ethylene pressure, add 0.100g finished catalyst B, pressurize to reactor with 144psi (993kPa) ethene.Reactor is remained under the situation of 90 ℃ and 144psi (993kPa), and described polymerization continues 30 minutes.By rapid cooling and emptying stopped reaction.Obtain 11.8g polyethylene (flow index (FI)=not flows, activity=641g polyethylene/mmol catalyzer atmh).

From above data as seen, under simulated condition, the present invention has the metal catalyst compounds that contains the 15th family's element of hydrocarbon leavings group (preferred aryl groups replace alkyl) of replacement more much higher than the same compound productive rate that halogen is arranged.

Embodiment among following examples part III uses and comprises the catalyst system of silicon oxide in conjunction with the aluminium activator.

Embodiment part III. comprises the catalyst system of silicon oxide in conjunction with aluminium

Preparation described in the embodiment part I of front [(2,4,6-Me ₃C ₆H ₂) NHCH ₂CH ₂] ₂NH (part) and [(2,4,6-Me ₃C ₆H ₂) NCH ₂CH ₂] ₂NH}Zr (CH ₂Ph) ₂(Zr-HN ₃).

Silicon oxide is in conjunction with aluminium (Si-O-Al (C ₆F ₅) ₂) preparation

In the 500ml round-bottomed flask, make the 40.686g silicon oxide (Davison 948,600 ℃ baked, available from W.R.Grace, Davison Division, Baltimore, Maryland) specimen suspension is in 300ml toluene.Add solid Al (C ₆F ₅) ₃(15.470g 24.90mmol), stirs mixture 30 minutes toluene.Mixture was left standstill 18 hours.Filter to isolate silicon oxide in conjunction with aluminium, drying is 6 hours under vacuum, and output is 49.211g.Al (C ₆F ₅) ₃Toluene is incorporated herein for reference by the preparation of method described in EP 0 694 548A1.

The preparation of catalyst A (being used for this embodiment part III)

To the 1.000g silicon oxide in 20ml toluene be added in in conjunction with aluminium (from top embodiment 4) Zr-HN3 in the 5ml toluene (0.076g, 0.124mmol).Mixture was stirred 30 minutes.Described silicon oxide by colourless become orange red.Filter to isolate described silicon oxide, drying is 6 hours under vacuum, and output is 1.051g.Final transition metal load is that 116 μ mol transition metal/g silicon oxide are in conjunction with aluminium.

The slurry phase ethene-hexene polymerization of embodiment part III-embodiment 1 usefulness catalyst A

Carry out slurry phase polymerisation at 1 liter of autoclave reactor being furnished with mechanical stirrer, being used for outside water jacket, the barrier film inlet and the vent line of controlled temperature and supplying with drying nitrogen and ethene regularly.Make the reactor drying, 160 ℃ of degassings down.Add Trimethylmethane (400ml) as thinner with gastight syringe, add the 35ml1-hexene, and the hexane solution of adding 0.7ml 25wt% trioctylaluminum is as scavenging agent.Reactor is heated to 60 ℃.Under ethylene pressure, add 0.100g finished catalyst A, pressurize to reactor with 78psi (538kPa) ethene.Reactor is remained under the situation of 60 ℃ and 78psi (538kPa), and described polymerization continues 30 minutes.By rapid cooling and emptying stopped reaction.Obtain 70.0g multipolymer (flow index (FI)=not flows, and activity=2320g polyethylene/mmol catalyzer atmh is mixed the 10.5wt%1-hexene).

Embodiment among following examples part IV uses the solution feed of the metal catalyst that contains the 15th family's element.

Embodiment part IV contains the solution feed of the metal catalyst of the 15th family's element

As among the embodiment part I of front the preparation [(2,4,6-Me ₃C ₆H ₂) NHCH ₂CH ₂] ₂(NH part or Compound I precursor) and [(2,4,6-Me ₃C ₆H ₂) NCH ₂CH ₂] ₂NH}Zr (CH ₂Ph) ₂(Compound I).

The preparation of catalyst A (being used for this embodiment part IV)

(1.5wt% toluene solution)

Annotate: following institute all carries out in glove box in steps.

1. taking by weighing the 100g pure toluene adds in 1 liter of Erlenmeyer flask of the stirring rod of being furnished with the teflon of being coated with.

2. add 7.28g tetrabenzyl zirconium.

3. solution is placed on the agitator, stirred 5 minutes.All solids is all in the pass into solution.

4. add the 5.42g Compound I.

5. add the 551g pure toluene again, mixture was stirred 15 minutes.Remaining solid not in the solution.

6. catalyst solution is poured in 1 liter of Whitey test specimen tube that clean purging crosses, labelled, from glove box, take out, be placed on the conservation zone and be used for operation.

Embodiment part IV-embodiment 1:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 40lbs/hr (18kg/hr), and hexene infeeds reactor with the speed of about 0.6lbs/hr (0.3kg/hr), and hydrogen infeeds reactor with the speed of 5mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 27PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1900PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693727.) the taper catalyzer syrup filling tip of aperture 0.041in. (0.11cm) is arranged in the aeration gas flow.The toluene solution of 1wt% catalyst A and promotor (MMAO-3A; the hexane solution of 1wt% aluminium; MMAO-3A is the n-heptane solution of modified methylaluminoxane; available from Akzo Chemicals; Inc.; trade(brand)name Modified Methylalumoxane type 3A is under the protection of US5 041 584) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 400:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 0.28dg/min (I ₂₁) and the unimodal polymerisation thing of 0.935g/cc character.Calculate residual zirconium 1.63ppmw based on the reactor mass balance.

Embodiment part IV-embodiment 2:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 40lbs/hr (18kg/hr), and hexene infeeds reactor with the speed of about 3.5lbs/hr (1.6kg/hr), and hydrogen infeeds reactor with the speed of 25mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 20PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1900PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693727.) the taper catalyzer syrup filling tip of aperture 0.041in. (0.11cm) is arranged in the aeration gas flow.The 1-hexene of the toluene solution of 1wt% catalyst A, 0.22PPH and promotor (MMAO-3A, the isopentane solution of 4wt% aluminium) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 746:1 that the relative quantity of control MMA0 and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 1.2dg/min (I ₂), 29.7dg/min (I ₂₁), 23.9I ₂₁/ I ₂The unimodal polymerisation thing of ratio and 0.9165g/cc character.Calculate residual zirconium 0.89ppmw based on the reactor mass balance.

Embodiment part IV-embodiment 3:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 105 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 40lbs/hr (18kg/hr), and hexene infeeds reactor with the speed of about 0.6lbs/hr (0.3kg/hr), and hydrogen infeeds reactor with the speed of 6mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 24PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1600PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693727.) the taper catalyzer syrup filling tip of aperture 0.055in. (0.14cm) is arranged in the aeration gas flow.The toluene solution of 1.5wt% catalyst A and promotor (MMAO-3A, the solution of 1.8wt% aluminium in 25% heptane/75% hexane) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 320:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 0.67dg/min (I ₂₁) and the unimodal polymerisation thing of 0.9358g/cc character.Calculate residual zirconium 2.33ppmw based on the reactor mass balance.

Embodiment part IV-embodiment 4:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 36lbs/hr (16.3kg/hr), and hexene infeeds reactor with the speed of about 3.5lbs/hr (1.6kg/hr), and hydrogen infeeds reactor with the speed of 28mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 18PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1900PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693727.) the taper catalyzer syrup filling tip of aperture 0.041in. (0.11cm) is arranged in the aeration gas flow.The 1-hexene of the toluene solution of 1wt% catalyst A, 0.22PPH and promotor (MMAO-3A, the isopentane solution of 4wt% aluminium) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 925:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 1.7dg/min (I ₂), 41.7dg/min (I ₂₁), 24.1I ₂₁/ I ₂Unimodal polymerisation thing with 0.917g/cc character.Calculate residual zirconium 0.94ppmw based on the reactor mass balance.

Embodiment part IV-embodiment 5:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 40lbs/hr (18kg/hr), and hexene infeeds reactor with the speed of about 0.6lbs/hr (0.3kg/hr), and hydrogen infeeds reactor with the speed of 3.5mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 22PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1500PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693727.) the taper catalyzer syrup filling tip of aperture 0.041in. (0.11cm) is arranged in the aeration gas flow.The toluene solution of 1wt% catalyst A and promotor (MMAO-3A, the hexane solution of 1wt% aluminium) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 450:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 0.10dg/min (I ₂₁) and the unimodal polymerisation thing of 0.931g/cc character.Calculate residual zirconium 1.36ppmw based on the reactor mass balance.

Embodiment part IV-embodiment 6:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 40lbs/hr (18kg/hr), and hexene infeeds reactor with the speed of about 0.5lbs/hr (0.23kg/hr), and hydrogen infeeds reactor with the speed of 4mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 20PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 2050PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693727.) the taper catalyzer syrup filling tip of aperture 0.041in. (0.11cm) is arranged in the aeration gas flow.The toluene solution of 1wt% catalyst A and promotor (MMAO-3A, the isopentane solution of 4wt% aluminium) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 1550:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 0.36dg/min (I ₂₁) and the unimodal polymerisation thing of 0.943g/cc character.Calculate residual zirconium 2.5ppmw based on the reactor mass balance.

Embodiment part IV-embodiment 7:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 40lbs/hr (18kg/hr), and hexene infeeds reactor with the speed of about 0.6lbs/hr (0.3kg/hr), and hydrogen infeeds reactor with the speed of 12mPPH.Ammonia infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 20PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 2050PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693727.) the taper catalyzer syrup filling tip of aperture 0.041in. (0.11cm) is arranged in the aeration gas flow.The toluene solution of 1wt% catalyst A and promotor (MMAO-3A, the isopentane solution of 4wt% aluminium) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 868:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 3.5dg/min (I ₂₁), 0.115dg/min (I ₂), 30.2I ₂₁/ I ₂The unimodal polymerisation thing of ratio and 0.949g/cc character.Calculate residual zirconium 2.5ppmw based on the reactor mass balance.

Embodiment part IV-embodiment 8:

Produce the alkene copolymer of ethene-in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 40lbs/hr (18kg/hr), and hexene infeeds reactor with the speed of about 1.1lbs/hr, and hydrogen infeeds reactor with the speed of 12mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 25PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1900PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693 727.) the taper catalyzer syrup filling tip of aperture 0.041in. (0.11cm) is arranged in the aeration gas flow.The toluene solution of 1wt% catalyst A and promotor (MMAO-3A, the isopentane solution of 4wt% aluminium) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 842:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 41.2dg/min (I ₂₁), 1.22dg/min (I ₂), 33.8I ₂₁/ I ₂The unimodal polymerisation thing of ratio and 0.940g/cc character.Calculate residual zirconium 2.77ppmw based on the reactor mass balance.

Embodiment part IV-embodiment 9:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 90 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 48lbs/hr, and hexene infeeds reactor with the speed of about 0.6lbs/hr (0.3kg/hr), and hydrogen infeeds reactor with the speed of 10mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 23PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1600PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693 727.) the taper catalyzer syrup filling tip of aperture 0.055in. (1.4cm) is arranged in the aeration gas flow.The toluene solution of 1.5wt% catalyst A and promotor (MMAO-3A, the solution of 1.8wt% aluminium in 25% heptane/75% hexane) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 265:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 0.3dg/min (I ₂₁) and the unimodal polymerisation thing of 0.933g/cc character.Calculate residual zirconium 2.38ppmw based on the reactor mass balance.

Embodiment part IV-embodiment 10:

Produce ethene-hexene copolymer in the 14in that water cooling heat exchanger is arranged (35.6cm) the pilot scale Gas-phase reactor of under 95 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Ethene infeeds reactor with the speed of about 45lbs/hr, and hexene infeeds reactor with the speed of about 0.6lbs/hr (0.3kg/hr), and hydrogen infeeds reactor with the speed of 6mPPH.Nitrogen infeeds reactor gas as a supplement with the speed of about 5-8PPH.Productivity is about 25PPH.Described reactor is furnished with inflation mechanism, the circulating current of the 1600PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693 727.) the taper catalyzer syrup filling tip of aperture 0.055in. (1.4cm) is arranged in the aeration gas flow.The toluene solution of 1.5wt% catalyst A and promotor (MMAO-3A, the solution of 1.8wt% aluminium in 25% heptane/75% hexane) on-line mixing before entering fluidized-bed by described syrup filling tip.It is 350:1 that the relative quantity of control MMAO and catalyzer makes the Al:Zr mol ratio.Also supply with nitrogen and iso-pentane to keep stable mean particle size to described syrup filling tip as required.Acquisition has nominal 0.4dg/min (I ₂₁) and the unimodal polymerisation thing of 0.934g/cc character.Calculate residual zirconium 2.27ppmw based on the reactor mass balance.

The data of the embodiment 1 to 10 of embodiment part IV are shown in the Table II.

Table II

Embodiment	Temperature ℃	H 2/C 2	C 6/C 2	I 2dg/nmin	I 21dg/min	Density g/cc	Remaining ZrPpmw
								1	85	0.0015	0.0043	N/a	0.28	0.935	1.63
2	85	0.008	0.0410	1.2	29.7	0.9165	0.89
								3	105	0.0015	0.0050	N/a	0.67	0.9358	2.33
4	85	0.0087	0.0405	1.7	41.7	0.917	0.94
								5	85	0.0006	0.0051	N/a	0.1	0.931	1.36
6	85	0.0023	0.0012	N/a	0.36	0.943	2.50
								7	85	0.0051	0.0013	0.115	3.5	0.949	2.50
8	85	0.0114	0.0154	1.22	41.2	0.940	2.77
								9	90	0.0015	0.0050	N/a	0.3	0.933	2.38
10	95	0.0015	0.0050	N/a	0.4	0.934	2.27

Embodiment part IV-embodiment 11:

Make embodiment 4 produces above the 300lbs (138kg) polyethylene (being called polymer A) on Werner-Fleiderer ZSK-30 twin screw extruder with 1000ppm Irganox ^TM1076 and 1500ppm Irgafos ^TM1068 compoundings under 200 ℃ melt temperature form pelletizing.Then with described pelletizing at the film that under melt temperature 390 ℉ (199 ℃), frost line height 24in (61cm), blow-up ratio 2.5 and die gap 60mil (1524 μ m), is blow molded into 1.0mil (25 μ m) on the Gloucester extrusion blow film line with the speed of 188lb/hr (85kg/hr).Test ESCORENE under the same conditions ^TMHD7755.10 (ExxonChemical Company in Mt.Belvue, traditional serial reaction device product of Texas) as a comparison.All films were all pressed 23 ℃, 50% humidity conditioning 40 hours.Data are shown among Table III and the IV.

Table III

Embodiment	Escorene TMLL3002.32	Polymer A 1.8g/10min MI	Escorene TMLL3001.63
				I2，g/10min	2	1076	1
I21/I2	29	24	27
				Pellet density g/cc	0.918	0.918	0.918
Head pressure psi (MPa)	2690(19)	2470(17)	3380(23)
				Engine load, %	43	31.2	50.4
Film thickness nil, (μ m)	1(25)	1(25)	1(25)
				Film density, g/cc	0.917	0.916	0.917
26inch (66cm) dart, g	136	168	149
				Elmendorf is torn g/il (g/ μ m) MD	310(12.7)	254(10.4)	223(9.1)
Elmendorf is torn g/mil (g/ μ m) TD	609(24.9)	630(25.7)	753(30.7)
				1% secant modulus psi (Mpa) MD	30430(210)	31580(218)	31320(216)
1% secant modulus psi (Mpa) TD	38950(269)	42120(290)	39750(274)
				Ultimate tensile strength psi (MPa) MD	7444(51)	8551(59)	8880(61)
Ultimate tensile strength psi (MPa) TD	6498(45)	9892(68)	6894(48)
				Ultimate elongation %MD	641	546	552
Ultimate elongation %TD	793	694	756
				45 ° of gloss	40	79	23
Mist degree %	22	4.4	20

Table IV

Embodiment	Polymer A 1.3MI	EXCEED TM350D60
			I 2，g/10min	1.35	1
I 21/I 2	23	16
			Pellet density g/cc	0.918	0.918
Head pressure psi (MPa)	3010(21)	3810(26)
			Engine load, %	37.2	56.7
Film thickness mil, (μ m)	1(25)	1(25)
			Film density, g/cc	0.916	0.916
26inch (66cm) dart, g	276	646
			Elmendorf is torn g/mil (g/ μ m) MD	219？	264？
Elmendorf is torn g/mil (g/ μ m) TD	616？	392？
			1% secant modulus psi (Mpa) MD	31100(214)	29040(200)
1% secant modulus psi (Mpa) TD	41470(286)	33050(228)
			Ultimate tensile strength psi (MPa) MD	9017(62)	9986(69)
Ultimate tensile strength psi (MPa) TD	7684(53)	8535(59)
			Ultimate elongation %MD	529	504
Ultimate elongation %TD	690	646
			45 ° of gloss	74	25
Mist degree %	5	23

Embodiment in following examples part of V uses the solution feed of the hybrid catalyst system that comprises the metal catalyst that contains the 15th family's element and big ligand metal cyclopentadienyl catalyst.

The embodiment part of V. comprise that the metal catalyst and the big ligand metal that contain the 15th family's element are luxuriant The solution feed of the hybrid catalyst system of catalyzer

Catalyzer 1

In this embodiment part of V, catalyzer 1 is as the three PIVALIC ACID CRUDE (25) indenyl zirconiums of implementing to prepare described in the I of falling the part (the big luxuriant type compound of ligand metal).

The preparation of catalyzer 1-1% hexane solution

Following institute all carries out in glove box in steps.

2. 1 liter of pure hexane is moved in 1 liter of Erlenmeyer flask of the stirring rod of being furnished with the teflon of being coated with.

5. add 6.67g three PIVALIC ACID CRUDE (25) indenyl zirconium dry powder.

6. solution is placed on the agitator, stirred 15 minutes.All solids is all in the pass into solution.

Solution is poured in 1 liter of Whitey test specimen tube that clean purging crosses, labelled, from glove box, take out, be placed on the conservation zone until being used for operation.

Catalyzer 2

Preparation described in embodiment part I [(2,4,6-Me ₃C ₆H ₂) NHCH ₂CH ₂] ₂NH part (ligand i) and [(2,4,6-Me ₃C ₆H ₂) NCH ₂CH ₂] ₂NH}Zr (CH ₂Ph) ₂(Compound I) is used for this embodiment part of V as catalyzer 2.

The preparation of catalyzer 2-1.5wt% toluene solution

Annotate: following institute all carries out in glove box in steps.

8. taking by weighing the 100g pure toluene adds in 1 liter of Erlenmeyer flask of the stirring rod of being furnished with the teflon of being coated with.

9. add 7.28g tetrabenzyl zirconium.

10. solution is placed on the agitator, stirred 5 minutes.All solids is all in the pass into solution.

11. add the 5.42g ligand i.

12. add the 551g pure toluene again, mixture stirred 15 minutes.Remaining solid not in the solution.

13. catalyst solution is poured in 1 liter of Whitey test specimen tube that clean purging crosses, label, from glove box, take out, be placed on the conservation zone and be used for operation.

Embodiment part of V-embodiment 1:

Produce ethene-hexene copolymer in the 14in pilot scale Gas-phase reactor that water cooling heat exchanger is arranged of under 85 ℃ and 350psig (2.4MPa) total reactor pressure, operating.Described reactor is furnished with inflation mechanism, the circulating current of the 1600PPH that has an appointment.(described inflation mechanism is the device that is used for producing at gas fluidized bed reactor poor pars granulosa, referring to US5 693 727.) the taper catalyzer syrup filling tip of aperture 0.055in. (0.14cm) is arranged in the aeration gas flow.Begin to add before the described catalyst charge, ethylene pressure is about 220psia (1.5MPa), and 1-hexene concentration is about 0.3mol%, and density of hydrogen is about 0.12mol%.

Make catalyzer 2 dissolvings form the 0.5wt% toluene solution, infeed in the reactor with 12cc/hr.Make in promotor (MMAO-3A, 1wt% aluminium) and the feeding line of described catalyzer 2 before reactor Al/Zr mixed in molar ratio with 400:1.Productivity is about 24lb/hr (10.9kg/hr).In addition, also to described syrup filling tip supply 5.0lbs/hr (2.3kg/hr) nitrogen and 0.1bls/hr (0.05kg/hr) 1-hexene and 0.2lb/hr (0.09kg/hr) iso-pentane.The flow index of polymkeric substance is 0.31, and density is 0.935g/cc.Then, make catalyst charge speed reduce to 6cc/hr catalyzer 2, the hexane solution of 0.125wt% catalyzer 1 is added in the described material feeding pipeline with 13cc/hr.Whole reinforced order is: add hexene and with catalyzer 1, catalyzer 2 solution blended MMAO, isopentanize and ammonias then.The Al/Zr of total system is about 500.In 6 hours of interpolation catalyzer 1, described bimodal polymers has nominal 12.9dg/min (I ₂₁), (melt flow compares I to 130MFR ₂₁/ I ₂) and 0.953g/cc density.The mean particle size of resin is 0.0479in (0.12cm).Measure residual zirconium 0.7ppmw by x-ray fluorescence.

All documents of mentioning herein all are incorporated herein for reference, comprise any priority documents and/or testing method.From above general description and specific embodiments as seen, though described and for example understand form of the present invention, under the situation that does not deviate from spirit and scope of the invention, can make various modifications.Use two or the multiple metallic compound that contains the 15th family's element and one or more big ligand metal ocene catalyst system and/or one or more traditional catalyst system all within the scope of the present invention.Therefore the present invention will be limited to this.

Claims (28)

1. continuous gas-phase polymerization method, be included in and make olefinic monomer in the single Gas-phase reactor and comprise activator, include first catalyzer of metallic compound of the 15th family's element and the catalyst composition of second catalyst compound mixes that the described metallic compound that contains the 15th family's element is expressed from the next:

Wherein M is a group-4 metal;

Each X is leavings group independently;

N is the oxidation state of M;

M is the formal charge that contains the part of Y, Z and L;

L is the 15th family's element;

Y is the 15th family's element;

Z is the 15th family's element;

R ¹And R ²Be C independently ₁To C ₂₀Alkyl or containing of maximum 20 carbon atoms of heteroatomic group is arranged, heteroatoms is selected from silicon, germanium, tin, lead and phosphorus;

R ³Do not exist or be alkyl, hydrogen, halogen or contain heteroatomic group;

R ⁴And R ⁵Be cycloalkyl, the ring-type aralkyl of aryl, cycloalkyl, the replacement of alkyl, aryl, replacement, the ring-type aralkyl or the polycyclic system of replacement independently;

Wherein optional R ¹And R ²Interconnection, and/or R each other ⁴And R ⁵Interconnection each other,

R ⁶And R ⁷Do not exist independently or be hydrogen, halogen, heteroatoms or alkyl,

Described second catalyst compound comprises Metallocenic compound, Ziegler-Natta catalyst, Philips's type catalyzer, vanadium catalyst or their mixture,

Wherein produce a kind of polyolefine, and make described polyolefinic melt index I by the consumption that changes second catalyst component ₂Change.

2. the process of claim 1 wherein that described second catalyst compound comprises Metallocenic compound, Ziegler-Natta catalyst, Philips's type catalyzer, vanadium catalyst or their mixture; Wherein said Ziegler-Natta catalyst comprises MR _x, M is the metal of the 4th to 6 family in the formula, and R is halogen or-oxyl, and X is the oxidation state of metal M; Philips's type catalyzer comprises CrO ₃, two luxuriant chromium, silyl chromate, chlorination oxygen chromium CrO ₂Cl ₂, 2 ethyl hexanoic acid chromium or acetylacetonate chromium Cr (AcAc) ₃Described vanadium catalyst comprises three halogenation vanadyl, alkoxyl group halogenation vanadyl and alkoxylate vanadyl, four halogenation vanadium and alkoxyl group halogenation vanadium, acetylacetonate vanadium or acetylacetonate vanadyl.

3. the process of claim 1 wherein R ⁴And R ⁵Be expressed from the next:

R wherein ⁸To R ¹²Be hydrogen, C independently ₁To C ₄₀Alkyl, halogen, heteroatoms or contain containing of 40 carbon atoms of heteroatomic group at most, wherein any two R ⁸To R ¹²Base can form cyclic group or heterocyclic group.

4. the process of claim 1 wherein that described second catalyst compound comprises the Metallocenic compound with following general formula:

L ^DMQ ₂(YZ)X _n

Wherein M is the 4th, 5 or 6 family's metals;

L ^DFor with the indenyl or the fluorenyl of M bonding;

Q ₂(YZ) form single electric charge polydentate ligand, wherein Q be selected from-O-,-NR-,-CR ₂-and-S-; Y is C; Z is selected from-OR ,-NR ₂,-CR ₃,-SR ,-SiR ₃,-PR ₂,-H and replacement or non-substituted aryl, condition be when Q be-during NR-, Z is selected from-OR ,-NR ₂,-SR ,-SiR ₃,-PR ₂With-H; R is the alkyl that contains 1-20 carbon atom;

N is 1 or 2, when n is 2 X be the univalent anion base or when n is 1 X be the dianion base.

5. the method for claim 3, wherein R ⁹, R ¹⁰And R ¹²Be methyl, ethyl, propyl group or butyl independently.

6. the method for claim 3, wherein R ⁹, R ¹⁰And R ¹²Be methyl, R ⁸And R ¹¹Be hydrogen.

7. the process of claim 1 wherein that M is a group-4 metal, L, Y and Z are nitrogen independently, R ¹And R ²Be alkyl, R ³Be hydrogen, R ⁶And R ⁷Do not exist.

8. the process of claim 1 wherein R ⁶And R ⁷Be alkyl.

9. the method for claim 4, wherein M is a group-4 metal.

10. the method for claim 2, wherein said metallic compound that contains the 15th family's element and described second catalyst compound exist with 20: 80 to 80: 20 mol ratio.

11. the process of claim 1 wherein that described activator is selected from aikyiaiurnirsoxan beta, modified alumoxane, non-coordination ion activator, the neutral activator of non-coordination and composition thereof.

12. the process of claim 1 wherein that described second catalyst compound comprises Metallocenic compound shown in the following general formula

L ^AL ^BMQn or L ^AAL ^BMQn

M is the 4th, 5 or 6 family's metallic elements in the formula;

L ^AAnd L ^BBe selected from cyclopentadienyl, tetrahydro indenyl, indenyl and fluorenyl;

Q is the single anion leavings group;

A is the divalent abutment that contains at least one the 13rd to 16 family's element; N is 0,1 or 2.

13. the process of claim 1 wherein described polyolefine form the notch tension test value by the test of ASTM F1473 method under 3.0MPa greater than 500 hours tubing.

14. the process of claim 1 wherein that described catalyst compound and/or activator compound add in the Gas-phase reactor in carrier fluid.

15. the method for claim 1, use Gas-phase reactor, wherein at least two kinds of catalyzer and at least a activator add in carrier fluid in the reactor, and every kind of catalyzer is activated independently, described catalyzer and activator are mixed before in adding described reactor in described carrier fluid.

16. the method for claim 15, wherein said catalyzer is sequentially activated.

17. the method for claim 15, wherein

I) described catalyzer is mixed in carrier fluid, activator is added in the described carrier fluid then; Or

Described catalyzer is mixed in carrier fluid, add then in the passage that links to each other with described reactor, described activator is adding in the described passage with the identical or different position of described catalyzer.

18. the method for claim 16, the described carrier fluid that wherein comprises described catalyzer and described activator is placed on the device that is used for described carrier fluid is added described reactor.

19. the method for claim 18 wherein before described activator is added described device, adds described catalyzer and described carrier fluid in the described device.

20. the method for claim 14, wherein said carrier fluid comprise the liquid stream that flows into or spray into described reactor.

21. the method for claim 19, wherein said carrier fluid comprise the liquid stream that flows into or spray into described reactor.

22. the method for claim 14, wherein at least a catalyzer, at least a activator and described carrier fluid are placed on the device that is used for adding described reactor, wherein after first kind of catalyzer and activator add described device, other catalyzer is added in the described device.

23. the method for claim 14, wherein

I) first mixture that will comprise at least a catalyzer adds in carrier fluid in the device that links to each other with described reactor, second mixture that will comprise at least a activator adds in carrier fluid in described and the device that reactor links to each other, after for some time, different catalyzer is added in carrier fluid in described and the device that reactor links to each other, then described catalyzer-activator composition is added described reactor; Or

At least a catalyzer (a) and at least a activator (a) are mixed in carrier fluid, at least a catalyzer (b) and at least a activator (b) are mixed in carrier fluid, wherein said catalyzer (b) and different and/or described activator of described catalyzer (a) (b) and described activator (a) difference, with in the device that two kinds of mixtures add with described reactor links to each other, then described mixture is added described reactor then; Or

Iii) after the device that the carrier fluid that comprises catalyzer (a) and activator (a) adds with described reactor links to each other, will comprise in the device that the carrier fluid adding is described with reactor links to each other of catalyzer (b) and activator (b); Or

First composition that iv) will comprise at least a catalyzer (a), at least one activator (a) and carrier fluid is placed in the device that links to each other with described reactor, second composition that will comprise at least a catalyzer (b), at least a activator (b) and carrier fluid adds after described first composition in described and the device that reactor links to each other, wherein said catalyzer (b) and/or described activator (b) are different with described catalyzer (a) and/or described activator (a), then blend compositions are added described reactor; Or

V) at least a catalyzer and carrier fluid are placed on the device that is used for adding described reactor, after described first catalyzer adds described device, other catalyzer and activator are added in the described device; Or

First composition that vi) will comprise at least a catalyzer (a), at least one activator (a) and carrier fluid adds in the reinforced device of described reactor, then second catalyzer is added described in the reinforced device of reactor in carrier fluid, again second activator is added describedly in the reinforced device of reactor in carrier fluid, then described total mixture is added described reactor.

24. the method for claim 14 wherein made described catalyst compound and/or activator mix before putting into described carrier fluid, and/or wherein said carrier fluid is a paraffinic hydrocarbons.

25. arbitrary method of claim 14 to 24, wherein said catalyst compound and/or activator compound are carried on the carrier.

26. comprising, the method for claim 25, wherein said activator contain the agent of aluminium Lewis acid activation shown in alkylaluminium cpd, aikyiaiurnirsoxan beta, modified alumoxane, non-coordination anion, borine, ionization borate compound and/or the following formula:

R _nAl(ArHal) _3-n

Wherein R is a single anion ligand;

ArHal is halogenated C ₆The polycyclic aromatic hydrocarbons of aromatic hydrocarbons or higher carbon number or two or more ring or condense the aromatics ring system that ring system directly links together wherein; With

N=1 to 2.

27. the process of claim 1 wherein that described alkene is ethene or propylene or ethene and at least a other monomer that 3 to 20 carbon atoms are arranged.

28. the method for claim 1, this method is used to produce multimodal polymer composition.

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