CN1335860A

CN1335860A - Olefin polymerization catalyst system, polymerization process and polymer therefrom

Info

Publication number: CN1335860A
Application number: CN 99814533
Authority: CN
Inventors: R·E·穆雷; S·茂森; C·C·威廉姆斯; D·J·施莱克
Original assignee: Univation Technologies LLC
Current assignee: Univation Technologies LLC
Priority date: 1998-12-18
Filing date: 1999-11-19
Publication date: 2002-02-13
Anticipated expiration: 2019-11-19
Also published as: BR9916313A; JP2002533483A; CN1241953C; NO20012982L; WO2000037511A3; AU2027200A; EP1144465A2; MXPA01006185A; WO2000037511A2; AU756833B2; CZ20012224A3; PL348825A1; AR025281A1; CA2350451A1; NO20012982D0

Abstract

This invention relates to an olefin polymerization catalyst system comprising at least one activator and one of: a) at least two transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, as described below as represented by formula (I), (II), (III) or (IV); b) the product of the combination of an activator and a transition metal catalyst based on bidentate ligands containing pyridine or quinolines moieties, such as those described as represented by formula (III) or (IV), that has been allowed to react prior to the introduction into the reactor, preferably for at least 15 minutes, and/or c) the product of combination of an additive and a transition metal catalyst based on bidentate ligands containing pyridine or quinoline moieties, such as those described below as represented by formula (I) or (II). This invention further relates to a polymer produced therefrom, particularly to unique polyethylene resins, more preferably bimodal high density polyethylene resins produced by this invention.

Description

Olefin polymerization catalyst system, polymerization process and polymkeric substance prepared therefrom

Invention field

The present invention relates to contain activator and based on the olefin polymerization catalyst system of the catalyzer of transistion metal compound, this transistion metal compound contains bitooth ligand, this part comprises pyridine or quinoline moiety and composition thereof, relates to the polymerization process and the polymkeric substance prepared therefrom that use this catalyst system.

Background of invention

The industrialization of going deep into of metallocenes polyolefin catalyst has caused the extensive concern that non-metallocene, homogeneous catalyst are designed.A kind of especially academic concern the in this field because the novel metalloid cyclopentadienyl catalyst can provide the easier method of preparation currently available products, and also can provide above the product of metalloscene catalyst ability and the chance of technology.In addition, specific non-cyclopentadienyl ligands is more economical, because the analogue of various replacements is easier to synthesize.

So, need new olefine polymerization catalyst in the art and by the distinct polymer of these Preparation of Catalyst.Also need catalyst system easily to carry out modification, to form the bimodulus product by in single catalyst, adding additive.In addition, need to determine to prepare single mode and the polyolefinic catalyzer of bimodulus.The present invention determines the catalyzer of a class uniqueness, and it can be used singly or in combination, to prepare unique polyolefine, particularly bimodulus polyolefine.

People such as WO96/23101, WO97/02298, WO96/33202 and Furhmann, Inorg.Chem.35:6742-6745 (1996) discloses nitrogenous single site catalyst systems.

USSN 09/103620, and is open on January 14th, 1999 with WO99/01460, discloses and used the transistion metal compound that contains bitooth ligand, and this part comprises pyridine or quinoline moiety and composition thereof, makes with activator to be used for olefin polymerization.Particularly [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] zirconium closes dibenzyl and modified methylaluminoxane makes up in gas phase [2-methyl isophthalic acid-phenyl-2-propoxy-], with preparation ethene hexene polymkeric substance.We have found that USSN 09/103620 can improve by direct adding additive, with from single Preparation of Catalyst bimodulus product.

For the US purpose, mention below with reference to document: US 4845067; US 4999327; JP1126111; US 4508842; With UK 1015054.

Summary of the invention

The present invention relates to a kind of olefin polymerization catalyst system, contain a kind of at least a activator and the following component:

A) at least two kinds of transition-metal catalysts based on the bitooth ligand that contains pyridine or quinoline moiety, as representing by following formula I, II, III or IV,

B) activator and combination product based on the transition-metal catalyst of the bitooth ligand that contains pyridine or quinoline moiety shown in formula III or IV, can react before being introduced into reactor preferably at least 15 minutes, and/or

C) additive and combination product based on the transition-metal catalyst of the bitooth ligand that contains pyridine or quinoline moiety are shown in I or II.

The invention further relates to polymkeric substance, particularly Du Te polyvinyl resin, more preferably the bimodulus high-density polyethylene resin for preparing by the present invention by this catalyst system preparation.

The accompanying drawing summary

Fig. 1-the 5th, the relation curve of the log value of weight-average molecular weight and dwt/d (logM) is used for the molecular weight distribution that measurement table 1 is tested.

Fig. 6 and 7 is volume removing chromatogram (SEC) figure of experiment in embodiment 11 and 12.

Fig. 8 is the SEC figure of the polymkeric substance that makes among the embodiment 14.

Fig. 9 is the SEC figure of embodiment 14 among the USSN 09/103620 (being disclosed as WO99/01460) that submitted on June 23rd, 1998.

Detailed Description Of The Invention

A. the present invention partly relates to olefin polymerization catalyst system, and this system contains at least a activator and at least two kinds of transition-metal catalysts based on the bidentate ligand that contains pyridine or quinoline part. This activator can be any known catalyst activator, is alkyl aluminum, aikyiaiurnirsoxan beta, modified alumoxane, poly-aikyiaiurnirsoxan beta, non-coordination anion, lewis acid, borine or its mixture in one embodiment.

The various methods that prepare aikyiaiurnirsoxan beta and modified alumoxane are arranged, non-limiting example is described in United States Patent (USP) 4665208,4952540,5091352,5206199,5204419,4874734,4924018,4908463,4968827,5308815,5329032,5248801,5235081,5157137,5103031,5391793,5391529,5693838,5731253 and 5731451 and European patent application EP-A-0 561 476, EP-B1-0 279 586 and EP-A-0 594-218, and the open WO 94/10180 of PCT, it all is incorporated herein by reference. MAO, modified methylaluminoxane, triisobutyl alumina alkane and poly-MAO are preferred activators.

Ionic compound (non-coordination anion) can comprise active proton or associate but not coordination or only some other cations of weak coordination with the residual ion of ionic compound. This compound and analog thereof are described in European patent application EP-A-0 570 982, Ep-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944, EP-A-0 277 003 and EP-A-0 277 004, and United States Patent (USP) 5153157,5198401,5066741,5206197,5241025,5387568,5384299 and 5502124, and on August 3rd, 1994 U.S. Patent Application Serial 08/285380 submitted, it all is incorporated herein by reference. Other activator comprise the open WO of PCT 98/07515 described those, for example three (2,2 ', 2 "-nine fluorine diphenyl) fluoaluminate all is incorporated herein by reference it. The combination of activator also can be considered for the present invention, and for example combination of aikyiaiurnirsoxan beta and ionization activator referring to the open WO 94/07928 of for example PCT and WO 95/14044 and United States Patent (USP) 5153157 and 5453410, all is incorporated herein by reference it. Equally, activation method is such as using radiation etc. also can consider to be used in the present invention activator.

In preferred embodiments, activator is selected from following material: three (2,2 '; 2 "-nine fluorine diphenyl) fluoaluminate, aikyiaiurnirsoxan beta, triphenyl borine, boron triethyl, three normal-butyl ammonium tetraethyl borates, triarylborane, three normal-butyl ammonium four (pentafluorophenyl group) boron or three perfluorophenyl boron, or diethyl aluminum chloride.

In one embodiment, the transition metal catalyst compound based on the bidentate ligand that contains pyridine or quinoline part is expressed from the next;

((Z) XA _t(YJ)) _qMQ _n(I) wherein M is selected from the 3-13 family of the periodic table of elements or the metal of group of the lanthanides and actinium series; Q is bonded on the M, and each Q is unit price, divalence or trivalent negatively charged ion; X and Y are bonded on the M; X and Y are carbon or heteroatoms independently, and prerequisite is that among X and the Y at least one is heteroatoms, and preferred X and Y are heteroatomss; Y is contained among the heterocycle J, and wherein J contains 2-50 non-hydrogen atom, preferred 2-30 carbon atom; Z is bonded on the X, and wherein Z contains 1-50 non-hydrogen atom, preferred 1-50 carbon atom, or silyl, and the alkyl silyl is trialkylsilkl for example, and preferred Z is the cyclic group that contains 3-50 atom, preferred 3-30 carbon atom; T is 0 or 1; When t was 1, A was the bridge joint group, connected among X, Y or the J at least one, preferred X and J; Q is 1 or 2; If Q is a monovalent anion, then n is that the oxidation state of M deducts q and deducts 1, if Q is a dianion, then n be (oxidation state of M-q)/2, if or Q be the trivalent negatively charged ion, then n is that (oxidation state of M-q)/3, n is the integer of 1-4 usually, depends on the oxidation state of M.

In one embodiment, if X is oxygen or sulphur, then Z chooses wantonly.In another embodiment, if X is nitrogen or phosphorus, then Z exists.In one embodiment, Z is aryl preferably, is more preferably the aryl of replacement.T is an oxygen in preferred embodiments, and is connected with alkyl, aryl or alkaryl.

In another embodiment, transition metal catalyst compound is expressed from the next:

((R ' _mZ) XA (YJR " _p)) _qMQ _n(II) wherein M is the metal that is selected from the 3-13 family of the periodic table of elements, preferred 4-12 group 4 transition metal, more preferably 4,5 or 6 group 4 transition metals, even more preferably 4 group 4 transition metals, for example titanium, zirconium or hafnium, most preferably zirconium;

Each Q is bonded on the M, and each Q is unit price, divalence or trivalent negatively charged ion.Preferred each Q is independently selected from halogen, hydrogen, alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrogenation carboxyl (hydrocarboxy) or has the phenoxy group of 1-20 carbon atom.Each Q can be amino, phosphide, sulfide, silyl alkyl, two ketone esters and carboxylicesters.Randomly, each Q can contain one or more heteroatomss, and more preferably each Q is selected from halogenide, alkyl and arylalkyl.Most preferably, each Q is selected from arylalkyl, for example benzyl.

X and Y are bonded on the M, and are carbon or heteroatoms independently, and prerequisite is that among X and the Y at least one is heteroatoms, and preferred X and Y are heteroatomss, and more preferably X and Y are independently selected from nitrogen, oxygen, sulphur and phosphorus, even more preferably nitrogen or phosphorus, nitrogen;

Y is contained among heterocycle or the member ring systems J.J contains 2-30 carbon atom, preferred 2-7 carbon atom, more preferably 3-6 carbon atom, most preferably 5 carbon atoms.Randomly, the heterocycle J that contains Y can contain other heteroatoms.J can be by R " group replaces R " group is independently selected from hydrogen or straight chain, side chain, cyclic alkyl or alkenyl, alkynyl, alkoxyl group, aryl or aryloxy.Equally, two or more R " group can be connected to form circular part, for example aliphatic series or aromatic ring.Preferred R " be hydrogen or aryl, most preferably R " be hydrogen.As R " be aryl and Y when being nitrogen, form the quinoline group.Randomly, R " can be connected with A;

Z is the alkyl that is connected with X, preferred Z is the alkyl that contains 1-50 carbon atom, preferred Z is the cyclic group that contains 3-30 carbon atom, preferred Z is replacement or the unsubstituted cyclic group that contains 3-30 carbon atom, randomly comprise one or more heteroatomss, more preferably Z is an aryl, most preferably the aryl of Qu Daiing, Z can be silyl or alkyl silyl in another embodiment, preferred trialkylsilkl;

Z can be replaced by R ' group, and wherein R ' group is independently selected from hydrogen or straight chain, branched-chain alkyl or cycloalkyl, alkenyl, alkynyl or aryl.Equally, two or more R ' groups can be connected to form circular part, for example aliphatic series or aromatic ring.Preferred R ' is the alkyl that contains 1-20 carbon atom, and more preferably R ' is methyl, ethyl, propyl group, butyl, amyl group etc., comprises its isomer, and more preferably R ' is a methyl, or primary, the second month in a season or tertiary hydrocarbon base, comprise sec.-propyl, the tertiary butyl etc., most preferably R ' is a sec.-propyl.Randomly, R ' group can be connected with A.Preferred at least one R ' is in the ortho position of X;

A be with X and J at least one, preferred both bridge joint groups of being connected.Bridge joint group A contains the 13-16 family element of one or more periodic table of elements.More preferably, A contains one or more 14 family's elements, and most preferably A is carbon-based group, dibasic carbon-based group or the vinyl that replaces; With

In formula (II), m and p are the integer of 0-5 independently, and preferred m is 2; If Q is a monovalent anion, then n is that the oxidation state of M deducts q and deducts 1, if Q is a dianion, then n be (oxidation state of M-q)/2, if or Q be the trivalent negatively charged ion, then n is that (oxidation state of M-q)/3, preferred n is the integer of 1-4; Q is 1 or 2, and when q is 2, two of formula (II) ((R ' _mZ) XA (YJR " _m)) via the mutual bridge joint of bridge joint group, preferably contain the bridge joint group of 14 family's elements.

In preferred embodiments, when the n among formula I or the II is 2 or 3, be hydrogenation carboxyl, boric acid ester or amino then except a Q group, second kind of catalyzer is identical with first kind of catalyzer.In particularly preferred embodiments, when the n among formula I or the II is 2 or 3, be alkoxide, phenates, acetylacetonate, carboxylicesters, cyclopentadienyl, fluorenyl or indenyl then except a Q group, second kind of catalyzer is identical with first kind of catalyzer.In another particularly preferred embodiment, when the n among formula I or the II is 2 or 3, then second kind of catalyzer is identical with first kind of catalyzer, except a Q group of second kind of catalyzer is the hydrogenation carboxyl adducts of the similar Q group on first kind of catalyzer, preferred alcohols salt adduct, boric acid ester, phenates adducts, acetylacetonate adducts, carboxylicesters adducts, amino adducts, cyclopentadienyl adducts, fluorenyl adducts or indenyl adducts.

In preferred embodiments, at least a transition metal catalyst compound is expressed from the next:

((Z) XA _t(YJ)) _qMQ _mT _s(III) wherein M is selected from the 3-13 family of the periodic table of elements or the metal of group of the lanthanides and actinium series; T is bonded on the M, and be 13-16 family element, preferred oxygen, boron, nitrogen, silicon, phosphorus, sulphur or aluminium, T can also contain one or more heteroatomic one or more C1 to C50 groups and is connected with optional, preferred T is hydrogenation carboxyl, boric acid ester group or amino, preferred alkoxide, phenates, acetylacetonate, or carboxylicesters or cyclopentadiene thing group for example cyclopentadienyl, fluorenyl and indenyl, Q is bonded on the M, and each Q is unit price, divalence or trivalent negatively charged ion; X and Y are bonded on the M; X and Y are carbon or heteroatoms independently, and prerequisite is that among X and the Y at least one is heteroatoms, and preferred X and Y are heteroatomss; Y is contained among the heterocycle J, and wherein J contains 2-50 non-hydrogen atom, preferred 2-30 carbon atom; Z is bonded on the X, and wherein Z contains 1-50 non-hydrogen atom, preferred 1-50 carbon atom, and preferred Z is the cyclic group that contains 3-50 atom, preferred 3-30 carbon atom, Z can be a silyl in addition, the preferred alkyl silyl; T is 0 or 1; When t was 1, A was the bridge joint group, connected among X, Y or the J at least one, preferred X and J; Q is 1 or 2; If Q is a monovalent anion, then m is that the oxidation state of M deducts q and deducts s, if Q is a dianion, then m be (oxidation state of M-q-s)/2, if or Q be the trivalent negatively charged ion, then m is the (oxidation state of M-q-s)/3, preferred m is the integer of 1-3, and s is 1,2 or 3, preferred 1 or 2.In one embodiment, when X was oxygen or sulphur, then Z chose wantonly.In another embodiment, if X is nitrogen or phosphorus, then Z exists.In a preferred embodiment, T is an oxygen, and is connected with alkyl, aryl or alkaryl.

In another embodiment, at least a transition metal catalyst compound is expressed from the next:

((R ' _mZ) XA (YJR " _p)) _qMQ _nT _s(IV) wherein M is the metal that is selected from the 3-13 family of the periodic table of elements, preferred 4-12 group 4 transition metal, more preferably 4,5 or 6 group 4 transition metals, even more preferably 4 group 4 transition metals, for example titanium, zirconium or hafnium, most preferably zirconium;

T is bonded on the M, and be 13-16 family element, preferred oxygen, boron, nitrogen, silicon, phosphorus, sulphur or aluminium, T can also contain one or more heteroatomic one or more C1 to C50 groups and is connected with optional, T is hydrogenation carboxyl, boric acid ester or amino preferably, preferred alkoxide, phenates, acetylacetonate, or carboxylicesters or cyclopentadiene thing group for example cyclopentadienyl, fluorenyl and indenyl.

Each Q is bonded on the M, and each Q is unit price, divalence or trivalent negatively charged ion.Preferred each Q is independently selected from halogen, hydrogen, alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrogenation carboxyl or has the phenoxy group of 1-20 carbon atom.Each Q also can be amino, phosphide, sulfide, silyl alkyl, two ketone esters and carboxylicesters.Randomly, each Q can contain one or more heteroatomss, and more preferably each Q is selected from halogenide, alkyl and arylalkyl.Most preferably, each Q is selected from arylalkyl, for example benzyl.

X and Y are C or heteroatoms independently, and prerequisite is that among X and the Y at least one is heteroatoms, and preferred X and Y are heteroatomss, more preferably are independently selected from nitrogen, oxygen, sulphur and phosphorus, even more preferably nitrogen or phosphorus, nitrogen;

Z is the alkyl that is connected with X, preferred Z is the alkyl that contains 1-50 carbon atom, preferred Z is the cyclic group that contains 3-30 carbon atom, preferred Z is replacement or the unsubstituted cyclic group that contains 3-30 carbon atom, randomly comprise one or more heteroatomss, Z can be silyl, alkyl silyl or trialkyl, and Z is not an aryl in another embodiment;

Z can be replaced by R ' group, and wherein R ' group is independently selected from hydrogen or straight chain, branched-chain alkyl or cycloalkyl, alkenyl or alkynyl.Equally, two or more R ' groups can be connected to form circular part, for example aliphatic series or aromatic ring.Preferred R ' is the alkyl that contains 1-20 carbon atom, and more preferably R ' is methyl, ethyl, propyl group, butyl, amyl group etc., comprises its isomer, and more preferably R ' is a methyl, or primary, the second month in a season or tertiary hydrocarbon base, comprise sec.-propyl, the tertiary butyl etc., most preferably R ' is a sec.-propyl.Randomly, R ' group can be connected with A.Preferred at least one R ' is in the ortho position of X;

In formula (IV), m and p are the integer of 0-5 independently, and preferred m is 2; S is the integer of 1-3; Q is 1 or 2, if Q is a monovalent anion, then n is that the oxidation state of M deducts q and deducts s, if Q is a dianion, then n be (oxidation state of M-q-s)/2, if or Q be the trivalent negatively charged ion, then n be (oxidation state of M-q-s)/3, and when q is 2, two of formula (IV) ((R ' _mZ) XA (YJR " _m)) via the mutual bridge joint of bridge joint group, preferably contain the bridge joint group of 14 family's elements.

In one embodiment, J is the pyridine in any following formula.

Transistion metal compound can prepare by any method well known in the art.USSN09/103620 for example, on June 23rd, 1998 submitted, and the preceding application number of being submitted by on July 2nd, 1,997 60/051581 requires right of priority, is disclosed as WO 99/01460, discloses the method for preparing these compounds.

In preferred embodiments, transistion metal compound is that [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium closes dibenzyl.In a further preferred embodiment, [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium closes dibenzyl and aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, more preferably modified methylaluminoxane is used in combination in gas phase or sludge phase reactor, with the preparation polyethylene, preferred high density polyethylene(HDPE).In a further preferred embodiment, non-coordination anion, for example three normal-butyl ammonium four (pentafluorophenyl group) boron or three perfluorophenyl boron, close dibenzyl and in gas phase or sludge phase reactor, be used in combination with [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium.In another embodiment, activator is selected from following material: three (2,2 '; 2 "-nine fluorine phenylbenzene) fluoaluminate, aikyiaiurnirsoxan beta, triphenyl-boron, triethyl-boron, three normal-butyl ammonium tetraethyl-borates, triaryl borate, three normal-butyl ammonium four (pentafluorophenyl group) boron, or three perfluorophenyl boron, or diethyl aluminum chloride.

In one embodiment, in the present invention's practice, select two or more catalyzer to prepare the product of expectation.Two or more catalyzer is selected from any catalyzer in the following formula.For example can select two kinds of different catalysts, maybe can make up from the compound of formula I or II with from the compound of formula III or IV from formula (I).Similarly, two kinds of different catalyzer in the formula IV range of definition can make up.In preferred embodiments, the compound from formula I or II uses with at least a compound from formula III or IV.Might obtain the bimodulus product by selecting the known catalyzer that can prepare different molecular weight.

In another embodiment, two kinds of catalyzer are added in the reactor respectively.

In preferred embodiments, first kind of catalyzer that selection is represented by formula I or II, wherein at least one Q group is not to contain the oxygen adducts, second kind of catalyzer is identical with first kind of catalyst system, except one, two or all three Q groups be with first kind of catalyzer in the identical Q group that exists contain the oxygen adducts.If for example select [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] zirconium closes tribenzyl as first kind of catalyzer, then to close dibenzyl can be second kind of catalyzer to [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium.

For the purposes of the present invention and claim, contain the oxygen adducts and be defined as O-R, wherein 0 is oxygen, and R optionally can contain one or more heteroatomic C ₁To C ₅₀Group.Preferred R group comprises the tertiary butyl, tert-pentyl, uncle's hexyl, sec.-propyl, 2-[2-methyl isophthalic acid-phenyl-propyl group], 2-[2-benzyl-butyl], 3-[3-benzyl-amyl group].Other possible R group comprises benzyl, methyl-benzyl, Ethylbenzyl etc.In another embodiment, contain the oxygen adducts and can be represented that wherein O is an oxygen by formula O-B-R, B is a boron, and R chooses wantonly to contain one or more heteroatomic C ₁To C ₅₀Group.Preferred R group comprises the tertiary butyl, tert-pentyl, uncle's hexyl, sec.-propyl, 2-[2-methyl isophthalic acid-phenyl-propyl group], 2-[2-benzyl-butyl], 3-[3-benzyl-amyl group].Other possible R group comprises benzyl, methyl-benzyl, Ethylbenzyl etc.

In preferred embodiments, two kinds of catalyzer, [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] zirconium closes tribenzyl and [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium closes dibenzyl, with aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, more preferably modified methylaluminoxane is used in combination in gas phase or slurry-phase reactor, with the preparation polyethylene, preferred high density polyethylene(HDPE) or new LDPE (film grade).In a further preferred embodiment, non-coordination anion, for example three normal-butyl ammonium four (pentafluorophenyl group) boron or three perfluorophenyl boron can with two kinds of catalyzer, i.e. [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] zirconium closes tribenzyl and [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium closes dibenzyl, in gas phase or sludge phase reactor, be used in combination, with preparation polyolefine, preferably polyethylene.

In preferred embodiments, two kinds of catalyst compound usually according to 0.001: 1 to about 10000: 1 ratio combination, preferred 0.5: 1 to 1000: 1. in preferred embodiments, the amount of first kind of catalyzer is about 0.5-99.5 weight %, the amount of second kind of catalyzer is about 99.5-0.5 weight %, weight with two kinds of catalyst weights rather than activator or carrier is benchmark, preferred first kind of catalyzer of 5-95 weight % and second kind of catalyzer of 95-5 weight %, preferred first kind of catalyzer of 10-90 weight % and second kind of catalyzer of 90-10 weight %.

In preferred embodiments, the amount of first kind of catalyzer is about 0.5-99.5 weight %, second kind of amount with the third catalyzer is about 99.5-0.5 weight %, weight with three kinds of catalyst weights rather than activator or carrier is benchmark, preferred first kind of catalyzer of 5-95 weight %, preferred first kind of catalyzer of 10-90 weight %.

B. the invention further relates to olefin polymerization catalyst system, this system contains the combination product of at least a activator and activator (as mentioned above) and the transition-metal catalyst of being represented by formula III or IV (as mentioned above), makes its preferred reaction at least 15 minutes before being introduced into reactor.In this embodiment, single transistion metal compound of being represented by formula III or IV can be used for preparing unique, preferred bimodulus polyolefine.Observe, temperature is obviously influential to the catalyzer of being represented by formula III or IV, and obviously makes other material.Though do not wish to be subject to any theory, it seems that this conversion provides the ability of preparation bimodulus product.Therefore, we notice, make more bimodulus product from catalyst system under higher temperature, and wherein a kind of transistion metal compound is used for Preparation of catalysts.Similarly observe, make transistion metal compound and activator reaction for some time, also can provide the system that can prepare bimodulus or multimodal polymer.Therefore, in preferred embodiments, make transistion metal compound and activator with reaction before alkene contacts at least 15 minutes, preferably at least 30 minutes, preferably at least 1 hour, preferably at least 4 hours.But, we are also noted that just [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] zirconium being closed tribenzyl and it are distinguished second kind of activation before being sprayed onto in the reactor, make very active catalyst system, this system also obviously makes the bimodulus resin.In another embodiment, polymerization is preferably carried out under at least 80 ℃ temperature, and preferably at least 85 ℃, preferably at least 90 ℃, preferably at least 100 ℃.

C. the invention further relates to olefin polymerization catalyst system, the transistion metal compound that contains at least a activator (as mentioned above) and additive and represent () combination product as mentioned above based on the bitooth ligand that contains pyridine or quinoline moiety by formula I or II.

This additive is alkoxy compound preferably.Alkoxy compound is defined as the compound of being represented by formula R=O, and wherein R is C ₁To C ₁₀₀Group, oxygen can connect on any point of R group.The R group can also contain heteroatoms except that 1-100 carbon atom.The preferred alkoxylated compound comprises ketone and aldehyde.Particularly preferred alkoxy compound comprises acetone, benzophenone, methyl ethyl ketone, metacetone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, diisopropyl ketone, methyl tertbutyl ketone, methyl phenyl ketone, pimelinketone, cyclopentanone, phenyl aldehyde, pivalyl aldehyde, ethyl n-propyl ketone, ethyl nezukone etc.

In preferred embodiments, additive and transition metal catalyst compound combination, consumption is that 0.5 weight % is to about 90 weight %, weight with transition metal catalyst compound and additive is benchmark, rather than the weight of any activator or carrier is benchmark, preferred 1 weight % is to about 80 weight %, more preferably 10-60 weight %.Additive can make up before adding polymerization reactor with transition metal catalyst compound (containing or do not contain activator).In one embodiment, additive is added in the online transition metal catalyst compound in the syringe.

In preferred embodiments, activator and transition metal catalyst compound (with additive reaction) were reacted 5 minutes before making up with alkene at least, preferred 10 minutes, more preferably 15 minutes.Notice, if transition metal catalyst compound simply with additive combination, directly add then in the reactor, then obtain less bimodulus product.If make additive and transistion metal compound reaction for some time, then can obtain more bimodulus product.

In preferred embodiments, make the combination before making up of additive and transition metal catalyst compound with activator.In another embodiment, transition-metal catalyst, alkene and activator are present in the polymerization reactor, and add additive.In embodiments, wherein after activator and transition metal catalyst compound have made up, add additive, and activator is aikyiaiurnirsoxan beta, then may needs the additive of additional quantity.

Different additives can be used for obtaining the Different Effects to resulting polymers.For example compare as additive, use metacetone to make polymkeric substance as additive with higher molecular weight with using methyl ethyl ketone.Similarly, compare as additive, use methyl ethyl ketone to make polymkeric substance as additive with higher molecular weight with using acetone.

In preferred embodiments, transition metal catalyst compound [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] zirconium closes tribenzyl and additive acetone and aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, more preferably modified methylaluminoxane is used in combination in gas phase or slurry-phase reactor, with the preparation polyethylene, preferred high density polyethylene(HDPE).In a further preferred embodiment, non-coordination anion, for example three normal-butyl ammonium four (pentafluorophenyl group) boron or three perfluorophenyl boron, zirconium closes tribenzyl and acetone is used in combination in gas phase or sludge phase reactor [1-N-2,6-diisopropyl phenyl amino] with transition metal catalyst compound [1-(2-pyridyl) N-1-methylethyl].

When adding wherein activator before or after transition 15 metallic compounds place reactor, additive can exist or not exist.In another preferred embodiment, two kinds of different transistion metal compounds and activator and additive are used in combination in same reactor.In another preferred embodiment, transition metal catalyst compound and activator are independent of in the additive adding reactor.Though do not wish to be subject to any theory, it seems additive and transition metal catalyst compound the reaction, so that another kind of active catalyst species to be provided.In embodiments of the invention, notice that temperature obviously influences two kinds of balances between the form catalyzer.It seems that higher temperature can promote transition metal catalyst compound to transform to second kind of catalyst substance in the presence of additive.Therefore, by the amount of selection additive and the temperature of combination and/or use thereof, can select desired final product.

In preferred embodiments, the amount that can make the catalyst component of lower molecular weight is 10ppm to 70 weight %, is benchmark with the weight of all catalyzer, rather than the weight of activator or carrier, preferred 100ppm to 8 weight %, even more preferably 1000ppm to 5 weight %.In another embodiment, the amount that can make the compound of lower molecular weight is 30-70 weight %, is benchmark with the weight of all catalyzer, rather than the weight of activator or carrier, preferred 40-60 weight %, even more preferably 45-55 weight %.

In another embodiment, the amount that can prepare the component of low molecular weight part can prepare the final polymer product of 20-70 weight %.

If use multiple catalyzer, then two or more catalyzer can be activated in the identical or different time, before or after entering reactor, and before or after placing on the carrier.In one embodiment, multiple catalyzer was activated before placing reactor by same activator.In another embodiment, a kind of catalyzer was activated before placing reactor, added second kind of catalyzer, did not randomly contain activator, identical activator or different activators.In another embodiment, catalyzer is attached on the identical carrier, is activated before placing reactor by same activator then.In another embodiment, two kinds of catalyzer were placed on the carrier before placing reactor then by identical or different activator activation.

Similarly, one or more catalyst systems or component can be attached on the organic or inorganic carrier.Usually carrier can be any solid, porous support.Common solid support material comprises talcum; Inorganic oxide, for example silicon-dioxide, magnesium chloride, aluminum oxide, silica-alumina; Polymer support, for example polyethylene, polypropylene, polystyrene; Deng.Preferred carrier comprises silicon-dioxide, clay, talcum, magnesium chloride etc.Preferred vector is with fractionized use.Before using, carrier is partially or completely dehydration preferably.Dehydration can be undertaken by the physics calcining, or is undertaken by all or part of activity hydroxy of chemical conversion.More details about how carrying attached catalyzer see also US 4808561, have wherein instructed and how to have carried attached metallocene catalyst system.Wherein used technology can be used among the present invention usually.

Catalyzer can place on other carrier of branch, maybe can place on the identical carrier.Similarly, activator can place on the carrier identical with catalyzer, maybe can place on other carrier of branch.Catalyzer/catalyst system and/or its component do not need to add in the reactor in the same way.For example, a kind of catalyzer or its component can be on carrier slurryization in reactor, and other catalyzer or component can the solution form provide.

In preferred embodiments, catalyst system is added in the reactor with solution or slurry form.Hydro carbons is used for solution or slurry.For example solution can be toluene, hexane, iso-pentane or its combination, for example toluene and iso-pentane or toluene and pentane.Typical solutions will be the 0.02-0.05 mol catalyst in the hydrocarbon carrier, preferred iso-pentane or hexane.

In another embodiment, the carrier that is used for catalyst system or its component is a supercutical fluid, for example ethane or propane.About supercutical fluid as the more details of the reinforced agent of catalyzer referring to EP 0 764 665 A2.

In a further preferred embodiment, a kind of or whole catalyzer and the maximum 6 weight % Metallic stearates combinations (preferred aluminum stearate, more preferably aluminium distearate) that with catalyzer, any carrier and stearate weight are benchmark, preferred 2-3 weight %.In another embodiment, the solution with Metallic stearates adds in the reactor.These reagent can carry out dry tumbling with catalyzer, and the solution form that maybe can contain or not contain catalyst system or its component adds in the reactor.In preferred embodiments, come roll cast with the catalyzer of activator combination with 1 weight % aluminium distearate and/or 2 weight % static inhibitor such as methoxylation amine, for example from ICISpecialties, the Kemamine AS-990 of the Witco of Bloomington Delaware.Metallic stearates and/or static inhibitor can slurryization be in reactor in mineral oil, and grind into powder is suspended in the mineral oil then, adds in the reactor, or directly is blown in the reactor as powder.

Can be introduced into this paper for your guidance referring to the USSN 09/113216 that submitted on July 10th, 1998 about the more details of using aluminum stearate type additive.Polymerization process of the present invention

Above-mentioned catalyzer and catalyst system are applicable to solution, gas phase or slurry phase polymerisation process or its combination, most preferably gas phase or slurry phase polymerisation process.

In one embodiment, the present invention relates to solution, slurry or gas phase polymerization, comprise that one or more contain 2-30 carbon atom, preferred 2-12 carbon atom, more preferably the monomer of 2-8 carbon atom carries out polymerization.Preferred monomer comprises one or more in ethene, propylene, butene-1, amylene-1,4-methyl-amylene-1, hexene-1, octene-1, decylene-1,3-methyl-amylene-1 and cycloolefin or its combination.Other monomer can comprise vinyl monomer, and diolefine is dienes for example, polyenoid, norbornylene, norbornadiene, vinyl norbornene, ethylidene norbornene monomer.Preferably make the homopolymer of ethene.In another embodiment, make ethene and one or more above-mentioned monomeric multipolymers.

In another embodiment, the comonomer polymerization different with at least two kinds of ethene or propylene forms terpolymer.Preferred comonomer be contain 4-10 carbon atom, more preferably 4-8 carbon atom 'alpha '-olefin monomers randomly with the combination of at least a diene monomers.Preferred terpolymer comprises combination, ethylene/butylene-1/ hexene-1 for example, ethylene/propene/butene-1, propylene/ethylene/hexene-1, ethylene/propene/norbornylene etc.

In particularly preferred embodiments, the inventive method relates to an ethene and at least a 4-8 of a containing carbon atom, preferably the comonomer of 4-7 carbon atom carries out polymerization.Particularly, comonomer is butene-1,4-methyl-amylene-1,3-methyl-amylene-1, hexene-1 and octene-1, most preferably hexene-1, butene-1 and octene-1.

Usually in gas phase polymerization process, use circulation continuously, wherein in a reactor system round-robin part, circulating current is also referred to as recirculated air or flow media, heats by heat of polymerization in reactor.Remove this heat in the circulation composition of cooling system from another part circulation by the reactor outside.Usually, in the phase fluidised bed processes that is used for preparing polymkeric substance, make and contain one or more monomeric air-flows and in the presence of catalyzer, under reaction conditions, circulate continuously from fluidized-bed.Discharge air-flow from fluidized-bed, and circulation turns back in the reactor.Simultaneously, discharge polymer product, and add fresh monomer to replace polymeric monomer from reactor.(, it all being incorporated herein by reference) referring to for example United States Patent (USP) 4543399,4588790,5028670,5317036,5352749,5405922,5436304,5453471,5462999,5616661 and 5668228.

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

Temperature of reactor in the gas phase process can from about 30 ℃ to about 120 ℃ of variations, preferably from about 60 ℃ to about 115 ℃, more preferably about 70 ℃ to about 110 ℃ scope, most preferably at about 70 ℃ extremely in about 95 ℃ scope.In another embodiment, when the needs high density polyethylene(HDPE), temperature of reactor is usually between 70-105 ℃.

Catalyzer or catalyst body tie up to the influence that productive rate in the gas phase system is subjected to the principal monomer dividing potential drop.The molar percentage of preferred principal monomer ethene or propylene, optimal ethylene is about 25-90 mole %, the branch of comonomer is pressed in about 20psia (138 kPas) to the scope of about 300 psia (517 kPas), preferred about 75psia (517 kPas) is to about 300 psia (2069 kPas), and this is the representative condition in the gas phase polymerization process.In some systems, exist comonomer also can improve productive rate.

In preferred embodiments, it is competent being used for reactor of the present invention, the inventive method prepares greater than 500lbs polymkeric substance/hour (227 kilograms/hour) to about 200,000lbs/ hours (90,900 kilograms/hour) or higher polymkeric substance, be preferably greater than 1000 lbs/ hours (455 kilograms/hour), more preferably greater than 10,000lbs/ hour (4540 kilograms/hour), even more preferably greater than 25,000 lbs/ hour (11300 kilograms/hour), further more preferably greater than 35,000lbs/ hour (15,900 kilograms/hour), further more preferably greater than 50,000lbs/ hour (22700 kilograms/hour), and be preferably greater than 65,000 lbs/ hours (29,000 kilogram/hour) extremely greater than 100,000 lbs/ hour (45,500 kilograms/hour) are most preferably greater than 100,000 lbs/ hour (45,500 kilograms/hour).

Can consider to be used for other gas phase process of the present invention and comprise described in United States Patent (USP) 5627242,5665818 and 5677375 those, and European patent application EP-A-0 794 200, EP-A-O802 202 and EP-B-634 421, it all is incorporated herein by reference.

Slurry phase polymerisation process usually use in about 1-50 normal atmosphere (15-735psi, 103-5068 kPa) scope pressure or even bigger, temperature is at 0 ℃ extremely in about 120 ℃ scope.In slurry polymerization, the suspension of solids polymkeric substance forms in the liquid polymeric diluent medium, to wherein adding ethene and comonomer and catalyzer.The suspension that will comprise thinner intermittently or from reactor, shift out continuously, separating volatile component from polymkeric substance wherein, and randomly after distillation, being recycled in the reactor.Used liquid diluent normally contains the alkane of 3-7 carbon atom, preferred branched alkane in polymerisation medium.Used medium should be a liquid under polymerizing condition, and is than inert.When using propane medium, this method 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, preferred polymerization technique of the present invention refers to the polymerization of particulate forms, or slurry process, wherein makes temperature keep below the temperature that polymkeric substance becomes solution.This technology is well known in the art, is described in for example United States Patent (USP) 3248179, and it all is incorporated herein by reference.In the method for particulate forms, preferred temperature at about 185 °F (85 ℃) to the scope of about 230 (110 ℃).Two kinds of preferred polymerization processes that are used for slurry process are to use annular-pipe reactor and a plurality of series connection, parallel connected stirred reactor, or its combination.The indefiniteness example of slurry process comprises continuous endless tube or stirring tank method.Other example of slurry process also is described in the United States Patent (USP) 4613484, and it all is incorporated herein by reference.

In another embodiment, slurry process operate continuously in annular-pipe reactor.Will be in Trimethylmethane as the catalyzer of slurry or as the catalyzer of unrestricted flow dry powder regularly in the injecting reactor endless tube, this endless tube itself is filled with the circulation slurry of polymer particle in the isobutane diluent that contains monomer and comonomer that is increasing.Hydrogen randomly can be used as molecular weight regulator and adds.Reactor is maintained at about under the pressure and the temperature in about 140 to about 220 (about 60 ℃ to about 104 ℃) scopes of 525psig to 625psig (3620 kPas to 4309 kPas), depends on required density polymer.Heat of reaction is removed by the endless tube wall, because most of reactor is a double fastener telescopic form.Make slurry clocklike discharging or be discharged to continuously in low pressure flash vessel, rotatory drier and the nitrogen purging tower of heating from reactor in the interval, to remove isobutane diluent and all unreacted monomer and comonomers.Then with the free powder compounding of hydrocarbon of gained, to be used for various uses.

In another embodiment, the reactor that is used for slurry process of the present invention is competent, and the inventive method preparation is greater than 2000lbs polymkeric substance/hour (907 kilograms/hour), more preferably greater than 5000 1bs/ hours (2268 kilograms/hour), most preferably greater than 10,000 1bs/ hours (4540 kilograms/hour).In another embodiment, be used for the slurry-phase reactor preparation of the inventive method greater than 15,000 lbs polymkeric substance/hour (6804 kilograms/hour), be preferably greater than 25,000 lbs/ hours (11,340 kilograms/hour) to about 100,000 lbs/ hour (45,500 kilograms/hour).

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

In another embodiment, in the slurry process of the present invention the concentration of ethene in the liquid reactor medium in about 1-10 weight % scope, preferably about 2-7 weight %, more preferably from about 2.5-6 weight %, most preferably from about 3-6 weight %.

Another kind of method of the present invention is this method, and preferred slurries or gas phase process do not exist or operate without any under the scavenging agent basically, for example triethyl aluminum, trimethyl aluminium, triisobutyl aluminium and tri-n-hexyl aluminum and diethyl aluminum chloride, dibutyl zinc etc.This method is described in open WO 96/08520 of PCT and the United States Patent (USP) 5712352, and it all is incorporated herein by reference.

In another embodiment, this method is carried out in the presence of scavenging agent.Typical scavenging agent comprises trimethyl aluminium, triisobutyl aluminium and excessive aikyiaiurnirsoxan beta or modified alumoxane.

The ratio of charging catalyst solution component can change, to change molecular weight and other performance.For example, change catalyst ratio and will change flow index, melting index, melt flow rate (MFR) and/or density.For example, in the system of the catalyzer of representing by formula I and the catalyst combination represented by formula IV, if improve the ratio of the catalyzer of representing by formula IV, then make the material of more lower molecular weight, and then improve flow index, change molecular weight distribution.In preferred embodiments, can make the feasible final polymer product that can prepare 45-65 weight % of amount of the catalyzer of lower molecular weight component.For some purposes, film for example, found 55-35 weight % (A) [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] combination of closing dibenzyl of zirconium (B) [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium of closing tribenzyl and 45-65 weight % is effective.

In addition-method of kind of change molecular weight is to add hydrogen to improve hydrogen ethene ratio in system.The method of control of density is to change co-monomer content.

This paper also provides control molecular weight distribution (M _w/ M _n), the method for flow index and/or density, be included in the technical scale Gas-phase reactor and (that is, have 1500 cubic feet (42.5 meters ³) or bigger volume) in online change temperature of reaction, and/or the catalyst ratio in the catalyst solution of intimate mixing, and/or density of hydrogen, and/or activator is to the ratio of transition metal aluminium/zirconium ratio for example.

Injection and mixing temperature also provide the means that change product property, because temperature effect activation and/or solvent evaporation, and therefore change the catalyzer composition, and then change final product.

Activatory order and also provide opportunity and change the chance that catalyzer is formed, and then change final product.For example containing (A) [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] zirconium closes tribenzyl and (B) [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium closes in the system of dibenzyl, and the methylaluminoxane of higher concentration will change the balance by these two kinds of catalyzer products therefroms.Higher concentration during this is included in activation and/or mixing and/or transportation and/or sprays into reactor.Similarly, we have noticed the hydrocarbon carrier that is increased in the catalyst charge, can improve the amount of gained lower molecular weight fraction.

Also can change product by changing temperature of reaction.We have noticed and have improved the amount that temperature of reaction can increase higher molecu lar weight component, and two kinds of patterns in volume removing chromatogram figure adjacent to each other unusually (that is, and when at a lower temperature with same system comparison, M _w/ M _nStep-down).

Also can be by changing temperature of reactor, before entering reactor, catalyst system changes the temperature of catalyst system, change the ratio of catalyzer, change the volume of carrier and/or transition metal component was contacted with solvent before being activated the agent activation and change molecular weight distribution activator.

In preferred embodiments, first kind of catalyzer is 5: 95 to 95: 5 to the ratio of second kind or other catalyzer, preferred 25: 75 to 75: 25, even more preferably 40: 60 to 60: 40.

In a further preferred embodiment, catalyst system is a liquid form, and is introduced in the interior poor district of resin particle of reactor.About how the liquid catalyst system being introduced the information in the poor district of particle in the fluidised bed polymerisation, see also US5693727, be introduced into this paper for your guidance.

Typical polymerization example is: at the hydrocarbon for example modified methylaluminoxane in hexane or the iso-pentane (about 1-10% aluminium) and [1-(2-pyridyl) N-1-methylethyl] [1-N-2 of 10-30 weight %, 6-diisopropyl phenyl amino] zirconium closes [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2 of tribenzyl and 70-90 weight %, 6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium closes dibenzyl and is suspended in the solution, dry then, with 2 weight % aluminium distearate roll casts, slurryization remains to temperature in about 85-100 ℃ the gas fluidized bed reactor then, wherein Al is about 500: 1 to about 1000: 1 to the ratio of Zr, ethylene gas is sprayed in the reactor, to keep the dividing potential drop of 70-100psi (0.5-0.7 MPa), make reactor move about 30 minutes then.Recovery has the polyethylene of 0.01-10dg/ minute melting index.

In preferred embodiments, the polyolefine that is reclaimed has the D-1238 at ASTM usually, condition E, and detecting down at 190 ℃ is 1 gram/10 minutes or littler melting index.In preferred embodiments, polyolefine is Alathon or multipolymer.Comonomer is C3 to C20 straight chain, side chain or cyclic monomer preferably, be C3 to C12 straight or branched alpha-olefin in one embodiment, preferred propylene, hexene, amylene, hexene, heptene, octene, nonene, decene, laurylene, 4-methyl-amylene-1,3-methyl-amylene-1,3,5,5-trimethylammonium hexene-1 etc.

In preferred embodiments, above-mentioned catalyst system is used to prepare high density polyethylene(HDPE), and its density is the 0.925-0.965 gram per centimeter ³(detecting) by ASTM 2839, and/or its melting index is 1.0 grams/10 minutes or littler (by ASTM D-1238, condition E detects down at 190 ℃).In another embodiment, above-mentioned catalyst system is used to prepare the 0.85-0.924 gram per centimeter ³Polyethylene.

In another embodiment, have by the polymkeric substance of the present invention preparation and be at least 10 molecular weight distribution (M _w/ M _n), preferably at least 15, preferably at least 20, even more preferably be at least 30.

In addition,, it is believed that the polymkeric substance by the present invention preparation has unique advantage though do not wish to be subject to any theory, i.e. two kinds of polymer product intimate blendings, so that two kinds of polymkeric substance in polymer particle are being evenly distributed when reactor is discharged.Be called straight polymer without processing, undressed granular polymer.Then straight polymer is become fraction by the standard screen cloth apart according to particle diameter (sieve analysis), method A or the PEG method 507 of ASTM D 1921 plastic materials.Fraction fraction title 10 orders that screen mesh size is collected＞2000 microns fraction 1 18 order 2000-1000 micron fractions 2 35 orders＜1000-500 micron fraction 3 60 orders＜500-250 micron fraction 4 120 orders＜＜125 microns fractions 6 of 250-125 micron fraction 5 dishes

Detect the physicals of indivedual fractions (fraction 1,4,6) then.Melting index is according to ASTM1238, condition E, 190 ℃ of detections.Degree of crystallinity detects with following embodiment 13 described X-ray diffractions.

The unique property of the polymkeric substance of the present invention's preparation is the not noticeable change of melting index of different fractions.In preferred embodiments, the variation of

fraction

1,4 and 6 melting index is not more than 20% relative value, preferably is not more than 15% relative value, preferably be not more than 10% relative value, preferably be not more than 8% relative value, preferably be not more than 6% relative value, preferably be not more than 4% relative value.Relative value refers to the mean value with respect to

fraction

1,4 and 6.

Another unique property of the polymkeric substance of the present invention's preparation is the not noticeable change of degree of crystallinity percentage of different fractions.In preferred embodiments,

fraction

1,4 and 6 the percentile variation of degree of crystallinity are not more than 6% relative value, preferably are not more than 5% relative value, preferably are not more than 4% relative value, preferably are not more than 3% relative value, preferably are not more than 2% relative value.Relative value refers to the mean value with respect to

fraction

1,4 and 6.

Another unique property of the polymkeric substance of the present invention's preparation is the M of different fractions _w/ M _nNot noticeable change.In preferred embodiments,

fraction

1,4,5 and 6 M _w/ M _nVariation be not more than 20% relative value, preferably be not more than 10% relative value, preferably be not more than 8% relative value, preferably be not more than 6% relative value, preferably be not more than 4% relative value, preferably be not more than 2% relative value.Relative value refers to the mean value with respect to fraction 1,4 and 6.M _nAnd M _wDetect being furnished with on the waters150 ℃ of GPC instrument of differential refractive index detector by gel permeation chromatography.The a series of by experiment narrow polystyrene standards of GPC post are proofreaied and correct, and calculate the molecular weight of described polymkeric substance with wide polyethylene standard State Bureau of Standardization 1496.

In another embodiment, the polymkeric substance of the present invention preparation has 8 or bigger M _w/ M _n, preferred 10 or bigger, preferred 12 or bigger.

In another embodiment, the parameter of resulting polymers is that crystallite morphology changes with particle diameter.Fraction 1 preferably has the aspect ratio of 0.5-1.5, and fraction 4 has the aspect ratio of 1.2-4, and fraction 6 has the aspect ratio of about 1.75-5, and prerequisite is that the difference of fraction is at least 0.3, and preferably at least 0.5, more preferably at least 1.0.In one embodiment, the aspect ratio of the aspect ratio＜fraction 6 of the aspect ratio＜fraction 4 of fraction 1.Aspect ratio is [＜110 〉/＜011 〉], as following

Embodiment 13 is described.

In a further preferred embodiment, polymkeric substance prepared in accordance with the present invention contains the low-molecular weight polymer (hang down and reach 50000 or lower, preferred 40000 or lower) of 10-90 weight %, preferred 20-80 weight %, more preferably 40-60 weight % is a benchmark with the weight of polymkeric substance.

In another embodiment, finding that prepared polyolefine has at least two kinds of molecular weight, is that benchmark exists greater than 20 weight % with the polymer weight.

In another embodiment of the invention, prepared polymkeric substance is bimodulus or multimode (on SEC figure).Bimodulus or multimode refer to that the SEC figure of polymkeric substance has two or more positive slopes; two or more negative slopes; with three or more flex point (flex point be second derive the point of curve when becoming negative value); perhaps this figure has a positive slope at least; a negative slope; a flex point, and just and/or the variation of negative slope greater than changing 20% of front slope.In another embodiment, SEC figure has a positive slope, a negative slope, a flex point, and M _w/ M _nBe 10 or bigger, preferred 15 or bigger, more preferably 20 or bigger.SEC figure is obtained at waters150 ℃ of GPC instrument being furnished with differential refractive index detector by gel permeation chromatography.The a series of by experiment narrow polystyrene standards of this post are proofreaied and correct, and calculate the molecular weight of described polymkeric substance with Mark Houwink coefficient.

Polyolefine can be made into film, moulded parts, sheet material, tubing etc.Film can form by any conventional art well known in the art, comprise extrude, coextrusion, laminated, blowing and curtain coating.Film can obtain by flat film or tubular process, and this method can be orientated in the single shaft direction on the membrane plane or on two orthogonal directions subsequently.The special preferred method that is used for polymer film forming is included on blowing and the cast film line to be extruded or coextrusion.

The film of gained can further contain additive, for example lubricant, anti-hard caking agent, antioxidant, pigment, filler, antifogging agent, UV light stabilizing agent, static inhibitor, polymer processing aid, neutralizing agent, lubricant, tensio-active agent, pigment, dyestuff and nucleator.Preferred additives comprises silicon-dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, lime carbonate, Metallic stearates, calcium stearate, Zinic stearas, talcum, BaSO ₄, diatomite, wax, carbon black, flame-retardant additive, low-molecular-weight resin, granulated glass sphere etc.Additive can significant quantity commonly used well known in the art exist, for example 0.001-10 weight %.

Has extremely outstanding appearance property with polymkeric substance prepared film of the present invention.This film has low gel content and/or has good turbidity and glossiness.In preferred embodiments, 45 ° of glossiness of 1 mil films (1.0 mils=0.25 micron) are 7 or bigger, preferred 8 or bigger, detect by ASTM D 2745.In preferred embodiments, the turbidity of 1 mil films (1.0 mils=0.25 micron) is 75 or littler, preferred 70 or littler, and by ASTM D 1003, condition A detects.

Embodiment

I ₂And I ₂₁By ASTM 1238, condition E and F detect.

The MFR melt flow rate (MFR) is detected by ASTM 1238.

BBF (butyl branching rate/1000 carbon atoms) is detected by infrared spectra, as described in United States Patent (USP) 5527752.

PDI (heterogeneity index) equals M _w/ M _n, detect by volume removing chromatogram.

M _nAnd M _wDetect being furnished with on the waters150 ℃ of GPC instrument of differential refractive index detector by gel permeation chromatography.The a series of by experiment narrow polystyrene standards of this GPC are proofreaied and correct, and with the molecular weight of the described polymkeric substance of Mark Houwink coefficient calculations.

Melting index (MI) is passed through according to ASTM 1238, and the step of condition E detects.

Melting index ratio (MIR) is I ₂₁To I ₂Ratio, detect according to the step of ASTM D 1238.

Density detects according to ASTM D 1505.

The preparation of embodiment 1 [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl] amine

In loft drier, 22.45 mmoles (6.34 gram) 2-acetylpyridine (2,6-diisopropyl phenyl imines) adding is equipped with in stirring rod and the membranous 250 milliliters of round-bottomed flasks.With this flask sealing, from loft drier, shift out, and place under the nitrogen purging.Add dry toluene (50 milliliters), and this part of stirring and dissolving.This container is quenched to 0 ℃ in wet ice bath.In 10 minutes, drip trimethyl aluminium (Aldrich, 2.0M is in toluene).Temperature of reaction must not be above 10 ℃.When finishing the adding trimethyl aluminium, make this mixture slowly be heated to room temperature.Be placed in the oil bath then, and be heated to 40 ℃ 25 minutes.Remove this container from oil bath, and place ice bath.The dropping funnel that will contain 100 milliliters of 5%KOH is connected on the flask.In 1 hour, alkaline matter is added dropwise in the reaction.This mixture is transferred in the other funnel.Remove the waterbearing stratum.Solvent layer washs with 100 ml waters, washs with 100 mL of saline then.Reddish-brown product liquid Na ₂SO ₄Drying, coupling vacuum stripping, and under high vacuum, place and spend the night.80 milliliters of reddish-brown liquid are transferred in 200 milliliters of Schlenk flasks that are equipped with stirring rod.The still head that will have dry-ice condenser is connected on the flask.This mixture is carried out vacuum distilling, obtain about 70 gram deep yellow viscous liquid products.

Embodiment 2[1-(2-pyridyl) N-1-methylethyl] [1-N-2.6-diisopropyl phenyl amino] zirconium closes three benzyls

The preparation of base

In dark place and dark loft drier, 5.0 mmoles (1.45 gram) part that makes among the embodiment 1 added be equipped with in 100 milliliters of Schlenk pipes of stirring rod.Part is dissolved in 5 milliliters of toluene.In second container that is equipped with stirring rod, add 5.5 mmoles (2.5 gram) tetrabenzyl zirconium and 10 milliliters of toluene.

Ligand solution is transferred in the tetrabenzyl zirconium solution.This container covers with aluminium foil, and it is at room temperature stirred in loft drier.After at room temperature 6 hours 80 milliliters of anhydrous hexanes are added in the reaction soln, and its stirring is spent the night.Reaction mixture is filtered from the frit of medium porosity, collect about 2 gram light yellow solids.

Embodiment 3[[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-first

Base-1-phenyl-2-propoxy-] zirconium closes the preparation of dibenzyl

To in the GC of oven drying, cooling, purging and sealing phial, adding 0.10 milliliter of anhydrous propanone.The GC phial is sealed in the hull shape phial, and puts into loft drier.In dark place and dark loft drier, 2.0 mmoles (1.3 gram) material that makes among the embodiment 2 and 9 milliliters of toluene are added be equipped with in 100 milliliters of Schlenk flasks of stirring rod.In the 2nd CC phial, add 2.0 mmoles (146 microlitre) acetone and 1.0 milliliters of toluene.By suction pipe [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] zirconium that acetone/toluene solution dropwise adds under stirring is closed in the tribenzyl solution.This container covers with aluminium foil, and its stirring at room temperature in loft drier is spent the night.The reaction soln coupling vacuum stripping is become the orange residue of viscosity.Add anhydrous hexane (20 milliliters), and with the resistates vigorous stirring, and then coupling vacuum stripping yellowly-orange glass.Add hexane again, and vigorous stirring.Container was placed refrigerator (24 ℃) about 2 hours.This mixture is filtered from the frit of medium porosity.Collect light yellow solid (0.8 gram).Slowly add acetone carefully, and good mixing is best.

Embodiment 4

The a series of bimodulus ethylene/hexene multipolymers of preparation in the laboratory scale sludge phase reactor, use by according to the title complex of the embodiment of the invention 2 and embodiment 3 preparations and modified methylaluminoxane (MMAO) promotor type 3A (available from Akzo chemical company, commodity are called modified methylaluminoxane type 3A, are disclosed as patent No. US5041584) mixed catalyst composition.

In each case, catalyst composition prepares by preparing the mixture of title complex in toluene from embodiment 2 and embodiment 3, contacting in the presence of 0.1 milliliter of 1-hexene with MMAO solution (7.0 weight %Al are in heptane) then.Polymeric reaction condition is 85 ℃, 85psi (586 kPas) ethene, and 43 milliliters of 1-hexenes, 0.5 micromole Zr, and the mol ratio of MMAO/Zr is 1000: 1.The title complex ratio is recently represented the mole of the title complex of embodiment 2 preparations by the title complex of embodiment 3 preparations.The result is as shown in table 1 below.

The active I of table 1 title complex ₂Dg/ minute every 1000C ' s of MFR BBF PDI ratio gram PE/ mmole

Catalyzer/100psi

C2/ hour 100: 0 139,765 162.2 1.82 6.28 11.1890: 10 291,765 13.49 61.66 10.08 25.8480: 20 175,529 0.05 1.027 7.54 23.7460: 40 235,765 0.0085 317.4 9.92 28.2450: 50 189,647 0.012 173.1 11.01 30.25

The resin of preparation carries out the volume removing chromatogram detection in the his-and-hers watches 1.The result clearly proves, along with the concentration from the title complex of embodiment 2 raises, high molecular weight component increases.Represent low and high molecular weight component in these bimodulus resins respectively from the relative quantity of the title complex of embodiment 3 and embodiment 2.This shows that two kinds of catalyzer are highly compatibles.

Embodiment 5

The ethene hexene copolymer prepares in 14 inches (35.6 centimetres) pilot plant Gas-phase reactor, and 85 ℃, 220psi (1517 kPas) operation down, this reactor has water cooling formula heat exchanger.Ethene adds with the speed of about 55 pounds of ethene/hour (25 kilograms/hour), hexene adds with 1.4 Pounds Per Hours (0.64 kilograms/hour), hydrogen adds with the speed of 0.021 Pounds Per Hour (0.01 kilogram/hour), to prepare the polymkeric substance of about 35 Pounds Per Hours (15.9 kilograms/hour).Total reactor pressure is 350psi (2413 kPas).Nitrogen exists with about 3-7 Pounds Per Hour (1.4-3.2 kilogram).Reactor is equipped with plenum system, is set to 1800 Pounds Per Hours (818.2 kilograms/hour), and the single hole that has internal diameter and be 0.055 inch (0.14 centimetre) is the nozzle syringe from the beginning.(plenum system is the equipment that is used for creating at gas fluidized bed reactor the poor district of particle.The more details of using about plenum system are referring to United States Patent (USP) 5693727) repeat this step, and in change temperature of reaction as shown in table 2, Al/Zr ratio, temperature of reaction, injection temperature or the hydrocarbon charging carrier one or more.

Table 2

Embodiment	The Rxn temperature	Weight % hangs down Mw	Catalyzer	Mw/Mn	Al: Zr ratio
Embodiment	The Rxn temperature	Weight % hangs down Mw	Catalyzer	Mw/Mn	Al: Zr ratio	A	85	60	3	14	??350∶1?∷?Al∶Zr
B	90	57	3	16	??360∶1?∷?Al∶Zr	A	85	60	3	14	??350∶1?∷?Al∶Zr
B	90	57	3	16	??360∶1?∷?Al∶Zr	C	95	51	3	12	??350∶1?∷?Al∶Zr
D	105	35	3	11	??350∶1?∷?Al∶Zr	C	95	51	3	12	??350∶1?∷?Al∶Zr
D	105	35	3	11	??350∶1?∷?Al∶Zr	E	85	22	60/40???2∶3		??450∶1?∷?Al∶Zr
F	85	70	3		??72∶1?∷?Al∶Zr	E	85	22	60/40???2∶3		??450∶1?∷?Al∶Zr

" weight % hangs down Mw " is the weight % of low molecular weight substance, characterized with normal state Gaussian solution convolution log value by volume removing chromatogram.

Embodiment 6

The catalyzer that makes with

embodiment

2 and 3 repeats above embodiment, and different is that polymerizing condition is 85 ℃, 220psi (1517 kPas) C ₂, 500: 1 Al/Zr, 10 milliliters/hour of catalyst charges, 300 milliliters/hour of MMAO chargings (2.3 weight %Al are in hexane).Change the ratio of two kinds of catalyzer.

Table 3 catalyst activity I ₂MFR density ratio (dg/ minute gram per centimeter of gram PE/ mmole ³2/3 Zr/ hour) 60,/40 15,651 0.196 51.47 0.945540/60 17,929 0.150 59.89 0.947520/80 16,905 0.165 63.45 0.94980/100 16,061 0.167 76.27 0.95180/20 40,048 0.150 52.08 0.9422

Embodiment 7

Two kinds of ethene hexene copolymers prepare in the Gas-phase reactor (volume is about 2000 cubic feet) of 8 feet (2.4 meters) diameters, and it is 38 feet (11.6 meters) that this reactor has bed height.Ethylene feed speed is about 8000-9000 Pounds Per Hour (3636-4090 kilogram/hour).The alkene feeding rate is about 200-230 Pounds Per Hour (a 90.0-104.5 kilogram/hour).Hydrogen feed speed is about 1-2 Pounds Per Hour (2.2-4.4 kilogram/hour).Multipolymer is with 8000-9000 Pounds Per Hour (3636-4090 kilogram/hour) preparation.30-60 Pounds Per Hour of (13.6-27.3 kilogram/hour) nitrogen is added in the reactor.Reactor is equipped with plenum system, be set to 50000 Pounds Per Hours (22727 kilograms/hour), and diameter is that 0.125 inch (0.32 centimetre) tapers to the triple jet that diameter is 0.05 inch (0.13 centimetre) centre hole, and distance is perpendicular to 0.30 inch two wide other hole of (0.76 centimetre) and 5/64 inch (0.20 centimetre) of nozzle end of air-flow.Recycle gas speed is about 2-2.2 feet per second (60-67 cel).Injection temperature is that experiment is 22 ℃ for the first time, and experiment is 80 ℃ for the second time.Catalyzer be catalyzer and the 2 weight % modified methylaluminoxane 3A of embodiment 3 preparation with Al: the Zr ratio is to make up at 150: 1.Experiment for the first time makes the ethene hexene copolymer with 44 weight % lower molecular weights part, and experiment for the second time makes the ethene hexene copolymer with 36 weight % lower molecular weights part.

Embodiment 8

Five kind 0.02 molar solution of gained compound in toluene is with the preparation of 80/20,60/40,40/60,20/80 and 0/100 ratio among the embodiment 2 and 3.According to the step of embodiment 5 with modified methylaluminoxane 3A as promotor with its polymerization.Bed tempertaure remains 85 ℃.Ethylene partial pressure is 220psi (1537 kPas), and Al: the Zr ratio is 500: 1.

Table 4

	80/20	60/40	40/60	20/80	0/100
	80/20	60/40	40/60	20/80	0/100	C6/C2 ratio (* 10 ^-3)	8.1-9.1	6.6-7.7	6.1-6.7	5.4-5.6	5.4-5.7
H2/C2 ratio (* 10 ^-3)	23.7-25.5	17.5-18.6	14.0	12.3-12.6	12.1-12.2	C6/C2 ratio (* 10 ^-3)	8.1-9.1	6.6-7.7	6.1-6.7	5.4-5.6	5.4-5.7
H2/C2 ratio (* 10 ^-3)	23.7-25.5	17.5-18.6	14.0	12.3-12.6	12.1-12.2	Throughput rate (pph)	28	26	26	26	27
Active gram PE/ mmole Zr/ hour	19000	17500	15000	16100	17500	Throughput rate (pph)	28	26	26	26	27
Active gram PE/ mmole Zr/ hour	19000	17500	15000	16100	17500	Melting index dg/ minute	0.15-0.26	0.17-0.26	0.13-0.34	0.12-0.17	0.16-0.21
Flow index dg/ minute	8.07-12.3	0.95- 12.88	8.81- 14.07	9.68- 10.95	12.53- 14.50	Melting index dg/ minute	0.15-0.26	0.17-0.26	0.13-0.34	0.12-0.17	0.16-0.21
Flow index dg/ minute	8.07-12.3	0.95- 12.88	8.81- 14.07	9.68- 10.95	12.53- 14.50	Melt flow MFR	39.87- 55.63	46.37- 64.39	32.96- 65.75	61.24- 81.87	70.73- 77.83
The density grams per milliliter	0.942- 0.944	0.945- 0.947	0.947- 0.950	0.950- 0.951	0.9951- 0.952	Melt flow MFR	39.87- 55.63	46.37- 64.39	32.96- 65.75	61.24- 81.87	70.73- 77.83

Embodiment 9[1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] [the 3-benzyl-

The 3-pentyloxy] zirconium closes the synthetic of dibenzyl

Metacetone (40 mmoles, 4.0 milliliters, Aldrich, propione, 99.5%, [86.13]) is dissolved in 96 milliliters of dry toluenes.Metacetone solution is slowly added in the stirred solution (400 milliliters, 0.125M is in toluene) of embodiment 2 gained title complexs.The gained solution stirring is spent the night.

Embodiment 10[1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] [the 2-benzyl-

The 2-butoxy] zirconium closes the synthetic of dibenzyl

Methyl ethyl ketone (40 mmoles, 3.6 milliliters, Aldrich, 2-butanone, 99.5%) is dissolved in 100 milliliters of dry toluenes.Methyl ethyl ketone solution is slowly added in the stirred solution (400 milliliters, 0.125M is in toluene) of embodiment 2 gained title complexs.The gained solution stirring is spent the night.

Embodiment 11

In loft drier, 1-hexene (0.1 milliliter, the aluminum oxide drying) is added in 4 drachm glass vial of oven drying.To add in the 1-hexene from the title complex (0.25 micromole, 2.0 microlitres, the 0.125M solution in toluene) of embodiment 2 and the title complex (0.25 micromole, 3.7 microlitres, the 0.067M solution in deuterate benzene) of embodiment 9 preparations, obtain pale yellow solution.Then MMAO type 3A (0.25 mmole) is added in the phial, obtain light yellow reaction soln.Reaction soln added contain in the reactor of 600 ml n-hexanes, 43 milliliters of 1-hexenes and 0.13 milliliter of (0.25 mmole) MMAO type 3A, and operation 30 minutes under 70 ℃, 85psi ethene and 10psi hydrogen.This reaction obtain 26.3 gram polyvinyl resins (active=polyethylene/mmole Zr/ hour/100psi ethene of 123765 grams, I2=28.49, I21=838, MFR=29.4, BBF=7.63).Volume removing chromatogram (SEC) shows following molecular weight result: Mn=12611, Mw=50585, PDI=4.01.SEC figure as shown in Figure 6.

Embodiment 12

In loft drier, 1-hexene (0.1 milliliter, the aluminum oxide drying) is added in 4 drachm glass vial of oven drying.To add in the 1-hexene from the title complex (0.25 micromole, the 0.125M solution in toluene) of embodiment 2 with from the title complex (0.25 micromole, the 0.080M solution in toluene) of embodiment 10, obtain pale yellow solution.Then MMAO type 3A (0.25 mmole) is added in the phial, obtain light yellow reaction soln.Reaction soln added contain in 1 liter of slurry-phase reactor of 600 ml n-hexanes, 43 milliliters of 1-hexenes and 0.13 milliliter of (0.25 mmole) MMAO type 3A, and operation 30 minutes under 70 ℃, 85psi ethene and 10psi hydrogen.This reaction obtain 30.7 gram resins (active=polyethylene/mmole Zr/ hour/100psi ethene of 144471 grams, I2=11.47, I21=468, MFR=40.8, BBF=7.53).Volume removing chromatogram (SEC) shows following molecular weight result: Mn=12794, Mw=62404, PDI=4.88.SEC figure as shown in Figure 7.

Embodiment 13

Step according to embodiment 5 prepares the ethene hexene copolymer (A) that density is about 0.946 grams per milliliter, different is adds from the catalyzer of embodiment 3 speed with 9 milliliters/hour, adds (90: 10 ratios) from the catalyzer of embodiment 2 with 1 milliliter/hour speed.Hexene with about 0.8-0.9 lbs (0.36-0.41 kilogram)/hour speed add.Ethene with about 41-43 pound (18.5-19.4 kilogram)/hour speed add.Hydrogen with about 17-20 milli pound (7.7-9.1 gram)/hour speed add, the hexane carrier is with about 100 milliliters/hour speed adding.The dividing potential drop of ethene is 120psi (827 kPas), and temperature of reactor is 75 ℃.Aluminium zirconium ratio is Al: Zr ∷ 300: 1.

Prepare another kind of ethene hexene copolymer (B) with same step, different is only will add from the catalyzer of embodiment 3 in the reactor (10 milliliters/hour), temperature of reactor is 95 ℃, hydrogen with 12-14 milli pound (5.4-6.4 gram)/hour the speed adding, ethene with 41-45 pound (18.5-20.3 kilogram)/hour speed add, the dividing potential drop of ethene is 220psi (827 kPas).The density of multipolymer is 0.951 grams per milliliter.

Prepare another kind of ethene hexene copolymer (C) with same step, different is only will add from the catalyzer of embodiment 3 in the reactor (12 milliliters/hour), temperature of reactor is 95 ℃, hydrogen with 12-13 milli pound (5.4-5.9 gram)/hour the speed adding, ethene with 44-47 pound (19.9-21.2 kilogram)/hour speed add, the dividing potential drop of ethene is 220psi (827 kPas), and the hexane carrier adds with 70 milliliters/hour speed.The density of multipolymer is 0.951 grams per milliliter.

Then in order to lower screen cloth with these multipolymer classifications: fraction fraction title 10 orders that screen mesh size is collected＞2000 microns fraction 118 order 2000-1000 micron fractions 235 orders＜1000-500 micron fraction 360 orders＜500-250 micron fraction 4120 orders＜＜125 microns fractions 6 of 250-125 micron fractions 5 dishes

Then such as among Table A, B, C and the D report characterize these fractions.Being used for X ray diffracting data experimental procedure of collecting and the technology that is used for degree of crystallinity percentage and crystallite morphological analysis summarizes

X ray diffracting data is collected:

The condition that all data is collected is, Siemens GADDS X-ray diffraction (XRD) device is equipped with CopperX x ray tube source (λ=1.54056 ), power supply at 40kV and 40mA is provided with operation down, the graphite monochromator, 0.3 millimeter collimator tube before sample, and multi-line general areas diffraction detector ((GADD), the distance of sample-detector is 15 centimetres.Big individual particles is bonded on the thin glass stick, and this makes particle suspension and rotates in electron beam, and is not subjected to the influence of glass stick or glue.Fine particle places the fine silica kapillary that is used for analyzing.All data gatherings are that electron beam carries out under 3 centimeters stop behind the sample at transmission mode.At three kinds of different diffractometers collection spectrum down is set, detector covers following 2 θ zones, and 4 °-34 °, 32 °-58 ° and 56 °-76 °, normally 600 seconds/district of collection time.(distortion is proofreaied and correct) proofreaied and correct in these three different zones, combines then to form the single spectrum that covers 4 ° of-76 ° of 2 θ.GADDS system in sample-detector distance 15 centimeters provides Debye 120 ° of radian visuals field of ring.This clearly illustrates that along the uniform strength of ring, expression is random uniform structure fully, shows not have preferred orientation or texture.

Fitting of a curve:

The whole distribution curve fit procedure that provided by the GADDS system are used for the match of spectrographic peak shape.For macroparticle, the air scattering decorative pattern under similarity condition deducted from experimental data before match, under the situation of small-particle, deducted from experimental data before match in conjunction with the spectrum of blank silica capillary and air scattering.Four kinds of components are used for the match diffraction data; (i) diffraction peak is that vacation-voigt profile-shape-function of 1 comes match with having hybrid parameter, (ii) amorphous peak comes match with the FWHM with peak (total half-breadth maximum value) with based on the Lorentzian profile-shape-function of the fixedly peak position of amorphous scattering analogue, and (iii) the para-crystal component is come match with the Pearson VII profile-shape-function with index 50 and (iv) is used for the linear fit of Compton scattering.

After Compton scattering cuts from data, the total diffracted intensity in pattern and three kinds of component matches, (1) amorphous intensity I _Am, (2) para-crystal component I _Para(3) crystalline diffraction peak I _XalFollowing formula is used to calculate the degree of crystallinity percentage:

Degree of crystallinity percentage=I _Xal/ (I _Am+ I _Para+ I _Xal) * 100

Crystallite dimension:

Crystallite dimension is used in the X-ray diffraction pattern of granular polyethylene resin { 110} and { calculating in the peak width of maximum strength under half of 011} reflection.These two values make can use the Scherrer equation to calculate the size of crystallite in given crystallographic direction:

Crystallite dimension (t)=0.9 λ/B ' cos θ _B

B '=B _{Detected value}-B _{Instrument broadens}Wherein λ is the wavelength of incident X-rays, and B ' is at half following gauged peak width radian of maximum strength (the instrument electron beam broadening component SRM of State Bureau of Standardization 660 Lanthanum Hexaboride sample detection), θ _BBe peak position, t is the crystalline size on the crystallographic direction aspect reflection.＜110〉reflection is provided at＜crystallite dimension information on 110〉direction, this direction is positioned at PE quadrature crystalline ab plane, similarly, 011} reflection is provided at＜crystallite dimension data on 011〉direction, this direction is positioned at the bc plane with c-axle component, thereby obtains the information about crystallite thickness.

So, the big I of the crystallite dimension on this both direction by be defined as＜110/＜011 shape-dependent constant provide about the morphologic information of crystallite.When this ratio was big, crystal was big in the ab plane, but thin in the bc plane, so they are " flaky ", when this ratio reached 1, two kinds of sizes were similar, thus crystallite morphology mostly be cube or spheric.

Table A provides the X ray diffracting data of all three kinds of study samples.Find that degree of crystallinity does not change with particle diameter, wherein small-particle has and the degree of crystallinity percentage identical than macroparticle.

Observe the crystallite dimension dull decline in the ab plane along with the increase of two kinds of sample particle diameters.On the contrary, observe crystallite dimension in bc plane (estimated value of c axle component) along with the increase of particle diameter dull increasing.

These results show that the crystallite shape changes along with particle diameter.Crystallite shape in small-particle is mostly to be " sheets ", aspect ratio [＜110 〉/＜011 〉] ≌ 2.2-3.5, along with particle becomes big, aspect ratio moves to the direction of ≌ 1-1.5, show crystallite mostly are cube/spheric.Therefore, along with size of particles is increased to 10 orders (＞2000 microns) from PAN (＜125 microns), the shape that is embedded in the crystallite phase farmland in the granular resin changes to cube/sphere from " sheet ".Particle can be considered as having classification type microtexture.

The example of observed character classification microtexture just in this catalyst system.Opposite configuration can in be formed centrally cube/spherical crystallite, be transformed into more the form of " sheet " then.Another kind of crystallite morphology can be " bar-shaped ", wherein shape-dependent constant become＜1.The possible classification microtexture of different crystallite morphologic distribution can causing wide regions, it can be controlled by catalyst type.

The X ray diffracting data of Table A-embodiment 13 samples

Sample	???％Xal	??％Para	??％Am	????FWHM ????(110)°	????FWHM ???(011)°	Xal size (110)	Xal size (011)
Sample	???％Xal	??％Para	??％Am	????FWHM ????(110)°	????FWHM ???(011)°	Xal size (110)	Xal size (011)	????A
10-order-1	????55.8	????4.3	???39.9	???0.4086	???0.5883	???197.7	??143.4	????A
10-order-1	????55.8	????4.3	???39.9	???0.4086	???0.5883	???197.7	??143.4	10-order-2	????56.2	????4.7	???39.1	???0.3926	???0.5883	???205.8	??143.4
10-order-3	????56.1	????5.3	???38.6	???0.4091	???0.5883	???197.5	??143.4	10-order-2	????56.2	????4.7	???39.1	???0.3926	???0.5883	???205.8	??143.4
10-order-3	????56.1	????5.3	???38.6	???0.4091	???0.5883	???197.5	??143.4	60-order-1	????55.6	????6.5	???37.8	???0.3557	???0.6647	???227.2	??126.9
????PAN-1	????53.7	????3.9	???42.4	???0.3510	???0.8433	???230.2	??100.0	60-order-1	????55.6	????6.5	???37.8	???0.3557	???0.6647	???227.2	??126.9
????PAN-1	????53.7	????3.9	???42.4	???0.3510	???0.8433	???230.2	??100.0	????PAN-2	????55.1	????5.6	???39.4	???0.3450	???0.7190	???234.2	??117.3
Av. (10 order)	????56.0	????4.8	???39.2	???0.40347	???0.5883	???200.4	??143.4	????PAN-2	????55.1	????5.6	???39.4	???0.3450	???0.7190	???234.2	??117.3
Av. (10 order)	????56.0	????4.8	???39.2	???0.40347	???0.5883	???200.4	??143.4	??Stdev(10)	????0.2	????0.50	???0.6	???0.0094	???0.0000	???4.7	??0.0
Av. (60/ dish)	????54.8	????5.3	???39.9	???0.3506	???0.7423	???230.5	??114.7	??Stdev(10)	????0.2	????0.50	???0.6	???0.0094	???0.0000	???4.7	??0.0
Av. (60/ dish)	????54.8	????5.3	???39.9	???0.3506	???0.7423	???230.5	??114.7	Stdev (60/ dish)	????1.0	????1.3	???2.3	???0.0054	???0.0916	???3.5	??13.6
????C								Stdev (60/ dish)	????1.0	????1.3	???2.3	???0.0054	???0.0916	???3.5	??13.6
????C								10-order-1	????61.9	????4.1	???34.0	???0.3028	???0.4678	???266.9	??180.3
10-order-2	????60.8	????3.1	???36.1	???0.2975	???0.4678	???271.6	??180.3	10-order-1	????61.9	????4.1	???34.0	???0.3028	???0.4678	???266.9	??180.3
10-order-2	????60.8	????3.1	???36.1	???0.2975	???0.4678	???271.6	??180.3	10-order-3	????60.0	????3.3	???36.7	???0.2970	???0.4695	???272.1	??179.6
60-order-1	????61.5	????5.3	???33.2	???0.2672	???0.5274	???302.4	??159.9	10-order-3	????60.0	????3.3	???36.7	???0.2970	???0.4695	???272.1	??179.6
60-order-1	????61.5	????5.3	???33.2	???0.2672	???0.5274	???302.4	??159.9	????PAN-1	????59.3	????3.8	???36.9	???0.2393	???0.5477	???337.7	??154.0
????PAN-2	????59.9	????6.9	???33.2	???0.2517	???0.5875	???321.0	??143.6	????PAN-1	????59.3	????3.8	???36.9	???0.2393	???0.5477	???337.7	??154.0
????PAN-2	????59.9	????6.9	???33.2	???0.2517	???0.5875	???321.0	??143.6	Av. (10 order)	????60.92	????3.5	???35.6	???0.2991	???0.4684	???270.2	??180.1
??Stdev(10)	????1.0	????0.5	???1.4	???0.0032	???0.0010	???2.9	??0.4	Av. (10 order)	????60.92	????3.5	???35.6	???0.2991	???0.4684	???270.2	??180.1
??Stdev(10)	????1.0	????0.5	???1.4	???0.0032	???0.0010	???2.9	??0.4	Av. (60/ dish)	????60.2	????5.3	???34.4	???0.2527	???0.5542	???320.4	??152.5
Stdev (60/ dish)	????1.1	????1.5	???2.1	???0.0140	???0.0306	???17.6	??8.3	Av. (60/ dish)	????60.2	????5.3	???34.4	???0.2527	???0.5542	???320.4	??152.5
Stdev (60/ dish)	????1.1	????1.5	???2.1	???0.0140	???0.0306	???17.6	??8.3	????B
10-order-1	????63.4	????7.9	???28.6	???0.2931	???0.3638	???275.9	??229.2	????B
10-order-1	????63.4	????7.9	???28.6	???0.2931	???0.3638	???275.9	??229.2	10-order-2	????65.2	????6.8	???28.0	???0.2278	???0.3638	???355.0	??229.2
10-order-3	????63.6	????6.8	???29.7	???0.2518	???0.5895	???321.2	??143.3	10-order-2	????65.2	????6.8	???28.0	???0.2278	???0.3638	???355.0	??229.2
10-order-3	????63.6	????6.8	???29.7	???0.2518	???0.5895	???321.2	??143.3	60-order-1	????62.7	????6.1	???31.2	???0.1800	???0.6451	???449.3	??131.0
????PAN-1	????64.7	????6.7	???28.6	???0.1768	???0.6451	???457.4	??131.0	60-order-1	????62.7	????6.1	???31.2	???0.1800	???0.6451	???449.3	??131.0
????PAN-1	????64.7	????6.7	???28.6	???0.1768	???0.6451	???457.4	??131.0	????PAN-2	????65.9	????6.9	???28.2	???0.1754	???0.6451	???461.1	??131.0
Av. (10 order)	????64.1	????7.2	???28.8	???0.2576	???0.4422	???317.4	??200.6	????PAN-2	????65.9	????6.9	???28.2	???0.1754	???0.6451	???461.1	??131.0
Av. (10 order)	????64.1	????7.2	???28.8	???0.2576	???0.4422	???317.4	??200.6	????Stdev(10)	????1.00	????0.7	???0.8	???0.0330	???0.1275	???39.7	??49.6
Av. (60/ dish)	????64.1	????6.6	???29.3	???0.1774	???0.6451	???455.9	??131.0	????Stdev(10)	????1.00	????0.7	???0.8	???0.0330	???0.1275	???39.7	??49.6
Av. (60/ dish)	????64.1	????6.6	???29.3	???0.1774	???0.6451	???455.9	??131.0	Stdev (60/ dish)	????1.2	????0.4	???1.6	???0.0024	???0.0000	???6.0	??0.0

For table B, C and D, CHMS refers to high molecular weight material (greater than 500,000), CLMS refers to low molecular weight substance (less than 3000), and VLD refers to very low density, the LD index and low density, HD refers to high-density, and CCLDI refers to crystallizable chain length dispersion index, and definition in United States Patent (USP) 5698427.CDI (50) refers to be used to weigh the composition dispersion index of how many polymkeric substance in intermediate value either side 25%.CDI (100) is used to weigh the composition dispersion index of how many polymkeric substance in intermediate value either side 50%.Two kinds form to distribute with temperature elution fractionation (TREF) technology for detection that raises, of (J.Polym.Sci.Phys.Ed. the 20th volume, p441-445 (1982)) such as Wild.At solvent for example 1,2, the elution solution in the 4-trichlorobenzene is at high temperature packed in the packed column with polymkeric substance.Make this post slowly be cooled to envrionment temperature with 0.1 ℃/minute.In slow process of cooling, the ethene polymers crystallization is to weighting material, so that increase branching (reduction degree of crystallinity) with the temperature reduction.After the cooling, with 0.7 ℃ of/minute reheat, constant solvent is flow through from this post this post, and with infrared concentration detector monitoring stream fluid.

CDI (100) is (CDBI) similar to " forming the Tile Width index " with CDI (50) index.CDBI is defined as, and has the copolymer chain weight % (referring to United States Patent (USP) 5470811) of the co-monomer content in 50% (± 25%) of the total mole of intermediate value co-monomer content.The different CDI (50) that are between CDBI and CDI (50) index use average branching rates (or co-monomer content) to replace the intermediate value co-monomer content.CDI (50) following by the TREF data by becoming the branching rate to determine the elution temperature inversion:

The branching rate is expressed as along the mean distance between the side chain of main polymer chain (at CH ₂In the unit), or be expressed as crystallizable chain length (L), wherein,

L = \frac{100}{BF}

With

\underset{BF - > 0}{limL} - > 2260

Use the distribution moment similar, can determine L to molecular weight distribution _iNumber average (L _n) and weight average (L _w) square, wherein: L _n=l/ Σ _i(w _i/ L _i) and L _w=Σ _iw _iL _iw _iBe the weight fraction of polymeric constituent i, this component has average main chain L at interval between two adjacent branch points _iSo, forming dispersion index or crystallizable chain length dispersion index (CCLDI) is defined as:

CCLDI=L _w/ L _nAverage branching rate is calculated by following formula:

\bar{BF} = Σ_{i = 1}^{\infty} W_{i} b_{i}

W wherein _iAnd b _iBe respectively weight fraction and the branching rate of every i of TREF color atlas.CDI (50) then by determine BF ± 25% in contained accumulating weight mark calculate.CDI (100) be defined as BF ± 50% in contained accumulating weight mark.

The characterization data of table B polymer A

Fraction	????1	????4	????5	????6
Fraction	????1	????4	????5	????6	????Mn	???10，604	???8，320	???8，815	???8，831
????Mw	??230，395	??227，935	??234，524	??247，901	????Mn	???10，604	???8，320	???8，815	???8，831
????Mw	??230，395	??227，935	??234，524	??247，901	????Mw/Mn	????19.2	????27.4	????26.6	????28.1
??CHMS(％)	????11.3	????13.1	????13.7	????14.5	????Mw/Mn	????19.2	????27.4	????26.6	????28.1
??CHMS(％)	????11.3	????13.1	????13.7	????14.5	??CLMS(％)	????1.3	????2.2	????2.0	????2.0
????VLD(％)	????3.5	????5.7	????3.6	????7	??CLMS(％)	????1.3	????2.2	????2.0	????2.0
????VLD(％)	????3.5	????5.7	????3.6	????7	????LD(％)	????5.8	????7.6	????4.9	????8.8
????HD(％)	????66.1	????62	????67.7	????64.1	????LD(％)	????5.8	????7.6	????4.9	????8.8
????HD(％)	????66.1	????62	????67.7	????64.1	????CCLDI	????10.9	????12.4	????10.6	????13.9
CDI(50)(％)	????9.8	????10.2	????8.7	????10	????CCLDI	????10.9	????12.4	????10.6	????13.9
CDI(50)(％)	????9.8	????10.2	????8.7	????10	CDL(100)(％)	????19.5	????20.2	????17.1	????19.7

The characterization data of table C polymer B

Fraction	????1	????3	????4	????5	????6
Fraction	????1	????3	????4	????5	????6	????Mn	??12，335	??11，486	??10，957	?10，408	??10，400
????Mw	??285，402	??236，008	??249，496	?244，990	??248，000	????Mn	??12，335	??11，486	??10，957	?10，408	??10，400
????Mw	??285，402	??236，008	??249，496	?244，990	??248，000	???Mw/Mn	????23.1	????22.9	????22.8	????23.5	????23.8
??CHMS(％)	????17.1	????15.9	????15.3	????15.0	????15.2	???Mw/Mn	????23.1	????22.9	????22.8	????23.5	????23.8
??CHMS(％)	????17.1	????15.9	????15.3	????15.0	????15.2	??CLMS(％)	????0.5	????0.6	????0.7	????0.7	????0.73
??VLD(％)	????4.2	????5.9	????2.5	????3.8	????2.3	??CLMS(％)	????0.5	????0.6	????0.7	????0.7	????0.73
??VLD(％)	????4.2	????5.9	????2.5	????3.8	????2.3	????LD(％)	????5.7	????7.6	????3.8	????5.5	????3.8
????HD(％)	????65.5	????60.9	????63.8	????58	????62.6	????LD(％)	????5.7	????7.6	????3.8	????5.5	????3.8
????HD(％)	????65.5	????60.9	????63.8	????58	????62.6	????CCLDI	????11	????11.7	????9.7	????10.5	????9.7
CDI(50)(％)	????11	????13.9	????12.5	????15.5	????14.1	????CCLDI	????11	????11.7	????9.7	????10.5	????9.7
CDI(50)(％)	????11	????13.9	????12.5	????15.5	????14.1	CDL(100)(％)	????20.6	????26.5	????23.5	????28.8	????25.3

The characterization data of table D polymkeric substance C

Fraction	????1	????4	????5	????6
Fraction	????1	????4	????5	????6	????Mn	??13.114	??13，081	???11.451	??11，328
????Mw	??243，241	??236，908	??219，370	??217，120	????Mn	??13.114	??13，081	???11.451	??11，328
????Mw	??243，241	??236，908	??219，370	??217，120	????Mw/Mn	????18.5	????18.2	????19.2	????19.2
??CHMS(％)	????13.7	????13.6	????12.6	????12.5	????Mw/Mn	????18.5	????18.2	????19.2	????19.2
??CHMS(％)	????13.7	????13.6	????12.6	????12.5	??CLMS(％)	????0.7	????0.6	????0.9	????1.0
????VLD(％)	????1.5	????2.5	????1.8	????3.9	??CLMS(％)	????0.7	????0.6	????0.9	????1.0
????VLD(％)	????1.5	????2.5	????1.8	????3.9	????LD(％)	????1.9	????3.3	????2.9	????4.5
????HD(％)	????84.3	????77	????78.6	????75.4	????LD(％)	????1.9	????3.3	????2.9	????4.5
????HD(％)	????84.3	????77	????78.6	????75.4	????CCLDI	????6.6	????8.4	????8.1	????9.2
CDI(50)(％)	????4.1	????9.2	????8.3	????11.8	????CCLDI	????6.6	????8.4	????8.1	????9.2
CDI(50)(％)	????4.1	????9.2	????8.3	????11.8	CDL(100)(％)	????9.3	????17.7	????16.11	????21.5

Embodiment 14

Preparation bimodulus ethylene/hexene multipolymer in the laboratory scale sludge phase reactor, (available from Akzo chemical company, commodity are called modified methylaluminoxane type 3A, are disclosed as patent No. US5 according to the title complex of the embodiment of the invention 3 preparation and MMAO type 3A promotor in use, 041,584).In this experiment, the title complex that MMAO3A was prepared with embodiment 3 in toluene before carrying out polyreaction reacted 4 hours.

In loft drier, toluene (0.4 milliliter, the aluminum oxide drying) is added in 4 drachm glass vial of oven drying.The title complex (2.0 micromoles, 0.067 milliliter of 0.030M solution in deuterate benzene) of embodiment 3 preparations is added in the toluene, obtain pale yellow solution.Then MMAO type 3A (1.0 mmoles, 0.52 milliliter, 1.89M, 7.0 weight % are in heptane solvent) is added in the phial, obtain the light yellow reaction soln of 0.002026M.Use the foil sealing phial then.After 4.0 hours, with 0.25 milliliter of (0.5 micromole ZR, 0.25 mmole MMAO) reaction soln adds in the reactor contain 600 ml n-hexanes, 43 milliliters of 1-hexenes and 0.13 milliliter of MMAO type 3A (7.0 weight % are in heptane solvent for 0.25 mmole, 1.89M).Reactor operation 30 minutes under 85 ℃ and 85psi (0.6 MPa) ethene.This reaction obtains 44.3 gram polyvinyl resins, and (active=208471 restrain polyethylene/mmole Zr/ hour/100psi ethene (when psi is converted into MPa, that psi is on duty with 0.0068948), I ₂=20.9, I ₂₁=824.1, BBF=9.5 butyl side chain/1000CH ₂Volume removing chromatogram (SEC) shows following molecular weight character: Mn=9123, Mw=104,852, Mw/Mn=11.49.SEC figure as shown in Figure 8.

Embodiment 15

In loft drier, MMAO type 3A (5.8 milliliters, 10 mmoles, 1.74M, 6.42 weight % are in heptane) is added in 4 drachm glass vial of oven drying.2-methyl isophthalic acid-phenyl-2-propyl alcohol (15.5 microlitres, 0.1 mmole) is dropwise added among the MMAO when stirring, obtain clear solution.

In loft drier, toluene (0.1 milliliter, the aluminum oxide drying) is added in 4 drachm glass vial of oven drying.The title complex (0.5 micromole, the 0.080M solution of 6.3 microlitres in toluene) of embodiment 2 preparations is added in the 1-hexene, obtain pale yellow solution.MMAO/2-methyl isophthalic acid-phenyl-2-propanol solution (0.25 mmole, 0.13 milliliter) with the epimere preparation adds in the phial then, obtains light yellow reaction soln.With phial in oil bath in 50 ℃ the heating 5 minutes, obtain the reddish-brown reaction soln.

Reaction soln added contain in 1 liter of slurry-phase reactor of 600 ml n-hexanes, 43 milliliters of 1-hexenes and 0.13 milliliter of (0.25 mmole) MMAO/2-methyl isophthalic acid-phenyl-2-propanol solution, and under 85 ℃ and 85psi (0.6 MPa) ethene, operated 30 minutes.This reaction obtains 16.3 gram polyvinyl resins, and (active=76706 restrain polyethylene/mmole Zr/ hour/100psi (0.7 MPa) ethene, I ₂=0.069, I ₂₁=2.15, MFR=31.1, BBF=7.71).Volume removing chromatogram (SEC) shows following molecular weight character: Mn=54637, Mw=-292411, PDI=5.35.

Embodiment 16

In loft drier, toluene (0.1 milliliter, the aluminum oxide drying) is added in 4 drachm glass vial of oven drying.The title complex (0.5 micromole, the 0.080M solution of 6.3 microlitres in toluene) of embodiment 2 preparations is added in the toluene, obtain pale yellow solution.MMAO/2-methyl isophthalic acid-phenyl-2-propanol solution (0.25 mmole, 0.13 milliliter) with the epimere preparation adds in the phial then, obtains light yellow reaction soln.With phial in oil bath in 50 ℃ the heating 15 minutes, obtain the reddish-brown reaction soln.

Reaction soln added contain in 1 liter of slurry-phase reactor of 600 ml n-hexanes, 43 milliliters of 1-hexenes and 0.13 milliliter of (0.25 mmole) MMAO/2-methyl isophthalic acid-phenyl-2-propanol solution, and under 85 ℃ and 85psi (0.6 MPa) ethene, operated 30 minutes.This reaction obtains 13.2 gram polyvinyl resins, and (active=62118 restrain polyethylene/mmole Zr/ hour/100psi (0.7 MPa) ethene, I ₂=0.248, I ₂₁=7.85, MFR=31.6, BBF=6.30).Volume removing chromatogram (SEC) shows following molecular weight character: Mn=42411, Mw=205990, PDI=4.86.

Above-mentioned all documents are incorporated herein by reference, comprise any priority document and/or detection method.From above-mentioned general description and specific embodiments as seen, though illustrated and described form of the present invention, can under the situation that does not exceed spirit and scope of the invention, carry out various improvement.Therefore, the present invention is not limited.

Claims

1. olefin Polymerization catalyst compositions, contain the combination product of at least a activator and a kind of following component:

A) at least two kinds of different transistion metal compounds, each free style I represents:

((Z) XA _t(YJ)) _qMQ _n(I) wherein M is selected from the 3-13 family of the periodic table of elements or the metal of group of the lanthanides and actinium series; Q is bonded on the M, and each Q is unit price, divalence or trivalent negatively charged ion; X and Y are bonded on the M; X and Y are carbon or heteroatoms independently, and prerequisite is that among X and the Y at least one is heteroatoms, and Y is contained among the heterocycle J, and wherein J contains 2-50 non-hydrogen atom; Z is bonded on the X, and wherein Z contains 1-50 non-hydrogen atom; T is 0 or 1; When t was 1, A was the bridge joint group, connected among X, Y or the J at least one; Q is 1 or 2; If Q is a monovalent anion, then n is that the oxidation state of M deducts q and deducts 1, if Q is a dianion, then n be (oxidation state of M-q)/2, if or Q be the trivalent negatively charged ion,, n be (oxidation state of M-q)/3, or

B) transistion metal compound of representing by following formula I and the product of additive, or

C) compound that is expressed from the next

((Z) XA _t(YJ)) _qMQ _mT _sWherein M is selected from the 3-13 family of the periodic table of elements or the metal of group of the lanthanides and actinium series; T is bonded on the M, and is 13-16 family element, and T can also contain one or more heteroatomic one or more C1 to C50 groups and is connected with optional, and Q is bonded on the M, and each Q is unit price, divalence or trivalent negatively charged ion; X and Y are bonded on the M; X and Y are carbon or heteroatoms independently, and prerequisite is that among X and the Y at least one is heteroatoms, and Y is contained among the heterocycle J, and wherein J contains 2-50 non-hydrogen atom, and Z contains 1-50 non-hydrogen atom, and t is 0 or 1; When t was 1, A was the bridge joint group, connected among X, Y or the J at least one, preferred X and J; Q is 1 or 2; If Q is a monovalent anion, then m is that the oxidation state of M deducts q and deducts s, if Q is a dianion, then m be (oxidation state of M-q-s)/2, if or Q be the trivalent negatively charged ion, then m is the (oxidation state of M-q-s)/3, s is 1,2 or 3, makes this compound reaction at least 15 minutes.

2. the composition of claim 1, wherein t is 1, Z is connected with one or more R ' groups, wherein R ' group is independently selected from hydrogen or straight chain, branched-chain alkyl or cycloalkyl, alkenyl, alkynyl or aryl, two or more R ' groups can be connected to form circular part, randomly, R ' group can be connected with A; J can be by two or more R " group replaces; R wherein " group is independently selected from hydrogen or straight chain, side chain, cyclic alkyl, or alkenyl, alkynyl, alkoxyl group, aryl or aryloxy, and two or more R " group can be connected to form circular part; randomly, and R " can be connected with A.

3. the composition of claim 1, wherein t is 1, Z is connected with one or more R ' groups, wherein R ' group is independently selected from hydrogen or straight chain, branched-chain alkyl or cycloalkyl, alkenyl, alkynyl or aryl, two or more R ' groups can be connected to form circular part, randomly, R ' group can be connected with A; J can be by two or more R " group replaces; R wherein " group is independently selected from hydrogen or straight chain, side chain, cyclic alkyl or alkenyl, alkynyl, alkoxyl group, aryl or aryloxy, and two or more R " group can be connected to form circular part; randomly, and R " can be connected with A.

4. the composition of claim 1, wherein T is hydrogenation carboxyl, boric acid ester group, amino or cyclopentadiene thing group.

5. the composition of claim 1, wherein T is alkoxide, acetylacetonate, carboxylicesters, phenates or its combination.

6. the composition of claim 1, wherein n is 2 or 3, and except a Q group be hydrogenation carboxyl, boric acid ester group or amino, second kind of catalyzer is identical with first kind of catalyzer.

7. the composition of claim 1, wherein n is 2 or 3, and except a Q group be alkoxide, phenates, acetylacetonate, carboxylicesters, cyclopentadienyl, fluorenyl or indenyl, second kind of catalyzer is identical with first kind of catalyzer.

8. the composition of claim 1, wherein n is 2 or 3, and except a Q group of second kind of catalyzer be the hydrogenation carboxyl adducts of similar Q group on first kind of catalyzer, second kind of catalyzer is identical with first kind of catalyzer.

9. the composition of claim 8, wherein said hydrogenation carboxyl adducts is pure salt adduct, boric acid ester or amino adducts, phenates adducts, acetylacetonate adducts or carboxylicesters adducts.

10. the composition of claim 1, wherein said additive is the alkoxy compound of being represented by formula R=0, wherein R is C ₁To C ₁₀₀Group, and oxygen can be along connecting on any point of R group, and the R group also can contain heteroatoms except that 1-100 carbon atom.

11. the composition of claim 1, wherein said additive comprise in acetone, benzophenone, methyl ethyl ketone, metacetone, methyl iso-butyl ketone (MIBK), methyl isopropyl Ketone, diisopropyl ketone, methyl tertbutyl ketone, methyl phenyl ketone, pimelinketone, cyclopentanone, phenyl aldehyde, pivalyl aldehyde, ethyl n-propyl ketone, the ethyl nezukone one or more.

12. the composition of claim 1, wherein M is titanium, zirconium or hafnium in all transistion metal compounds.

13. the composition of claim 1, wherein each Q is independently selected from boric acid ester, halogen, hydrogen, alkyl, aryl, alkenyl, alkylaryl, arylalkyl, hydrogenation carboxyl or has phenoxy group, amino, phosphide, sulfide, silyl alkyl, two ketone esters and the carboxylicesters of 1-20 carbon atom, and/or X and Y are nitrogen, oxygen, sulphur or phosphorus independently, and/or Z is aryl, and/or J is a pyridine.

14. the composition of claim 1, wherein said two kinds of different transistion metal compounds are [1-(2-pyridyl) N-1-methylethyl] [1-N-2,6-diisopropyl phenyl amino] zirconium closes tribenzyl and [[1-(2-pyridyl) N-1-methylethyl]-[1-N-2,6-diisopropyl phenyl amino]] [2-methyl isophthalic acid-phenyl-2-propoxy-] zirconium closes dibenzyl.

15. the composition of claim 1, wherein said activator are aikyiaiurnirsoxan beta, non-coordination anion or modified methylaluminoxane.

16. the method for an olefin polymerization comprises making alkene and contacting according to each catalyst composition among the claim 1-15.

17. the method for claim 26, wherein said alkene comprise that one or more have the monomer of 2-30 carbon atom.

18. the method for claim 26, wherein said alkene comprise one or more the combination in independent ethene or ethene and propylene, butene-1, amylene-1,4-methyl-amylene-1, hexene-1, octene-1, decylene-1 and the 3-methyl-amylene-1.

19. claim 16,17 or 18 method wherein change temperature of reactor, so that

The Mw/Mn of resulting polymers changes with the polymer phase ratio that makes before changing temperature.

20. claim 16,17 or 18 method wherein changed the temperature of this catalyst system, so that the Mw/Mn of resulting polymers changes with the polymer phase ratio that makes before changing temperature before catalyst system is introduced reactor.

21. claim 16,17 or 18 method wherein change the ratio of activator to catalyzer, so that the Mw/Mn of resulting polymers changes with the polymer phase ratio that makes before changing this ratio.

22. claim 16,17 or 18 method, wherein first kind of catalyzer is 5: 95 to 95: 5 to the ratio of second kind of catalyzer.

23. claim 16,17 or 18 method further comprise a kind of molecular weight distribution (M that is used to control _w/ M _n), the method for flow index and/or density, be included in online change temperature of reaction in the Gas-phase reactor of 1500 cubic feet or more volume, and/or the catalyst ratio in the catalyst solution of intimate mixing, and/or density of hydrogen, and/or activator is to the ratio of transition metal.

24. polymkeric substance by each method preparation among the claim 16-23.

25. have M _w/ M _nBe 10 or bigger polyolefine, wherein the polyolefine fraction 1,4 and 6 melting index is with respect to fraction 1, the variation of 4 and 6 mean values is not more than 20%, and wherein fraction 1,4 and 6 obtain with lower screen cloth by using: fraction fraction title 10 orders＞2000 microns fraction 1 181 order 2000-1000 meter levels that screen mesh size is collected divide 2 35 orders, and the 1000-500 meter level divides 3 60 orders＜500-250 micron fraction 4 120 orders＜250-125 micron fraction 5 to coil＜125 microns fractions 6

26. the polyolefine of claim 25, wherein this polyolefine is the multipolymer of Alathon or ethene and C3 to C20 straight chain, side chain or cyclic olefin.

27. the polyolefine of claim 25, wherein this polyolefine is ethene and propylene, butylene, hexene, amylene, heptene, octene, nonene, decene, 4-methyl-amylene-1,3-methyl-amylene-1,3,5, the multipolymer of one or more in 5-trimethylammonium hexene-1 and the laurylene.

28. claim 25,26 or 27 polyolefine, wherein

A) polyolefine fraction 1,4 and 6 degree of crystallinity percentage are not more than 6% with respect to the variation of fraction 1,4 and 6 mean values, and/or

B) polyolefine fraction 1,4 and 6 Mw/Mn are not more than 20% with respect to the variation of fraction 1,4 and 6 mean values, and/or

C) aspect ratio of fraction 1 is 0.5-1.5, and the aspect ratio of fraction 4 is 1.2-4, and the aspect ratio of fraction 6 is about 1.75-5, and prerequisite is that the aspect ratio of fraction differs at least 0.3.

29. the polyolefine of claim 28, the aspect ratio of wherein said fraction differs at least 0.5, preferably differs at least about 1.0.

30. the polyolefine of claim 28, wherein Mw/Mn is 20 or bigger.

31. one kind is carried out blowing, extrudes or film that curtain coating makes by the polyolefine according to each preparation among the claim 24-30.

32. one kind is carried out the moulded parts that blowing or extrusion molding make by the polyolefine according to each preparation among the claim 24-30.

33. the polyolefine of claim 24-30, wherein to have a positive slope, negative slope, flex point and Mw/Mn be 20 or bigger to SEC figure.

34. the polyolefine of claim 24-30, wherein to have two or more positive slopes, two or more negative slope, three or more flex point and Mw/Mn be 10 or bigger to SEC figure.

35. the polyethylene of claim 24-30, wherein SEC figure has one or more positive slopes, one or more negative slope, one or more flex point, Mw/Mn is 10 or bigger, and on any oblique line slope variation with change before slope be in a ratio of 20% or bigger.