CN104231125B - Load type non-metallocene catalyst, its preparation method and application thereof - Google Patents

Abstract

The present invention relates to a kind of load type non-metallocene catalyst and preparation method thereof.Described load type non-metallocene catalyst has the features such as catalysis activity is high, copolymerization effect is notable.The invention still further relates to the application in alkene homopolymerization/copolymerization of the described load type non-metallocene catalyst, the feature such as the alkene homopolymerization/copolymerization thing thus manufactured has that particle shape is good, narrow molecular weight distribution, oligomer and fine powder content reduction.

Description

Load type non-metallocene catalyst, its preparation method and application thereof

The application is based on " country's 11th Five-Year supporting plan problem " item understudied.This project has obtained the height of the Ministry of Science and Technology Degree is paid attention to and supports energetically, and its target is the polyolefin catalyst technology of new generation being formed and having independent intellectual property right, and improves Domestic Related product unification, improves China's polyolefin kind class, promotes that it is to variation, seriation, customizations, height The direction of performance-based is developed.

Technical field

The present invention relates to a kind of non-metallocene catalyst.Specifically, the present invention relates to a kind of load type non-metallocene urge Agent, its preparation method and the application in alkene homopolymerization/copolymerization thereof.

Background technology

The non-metallocene catalyst that nineteen nineties middle and late stage occurs, owing to occurring on the non cyclopentadienyl catalyst time After metallocene catalyst, be therefore otherwise known as " after cyclopentadienyl " olefin polymerization catalysis.It has similar to metallocene catalyst Feature, can customize polymer as required, and cost is relatively low.The central atom of non-metallocene catalyst includes almost institute Some transition metals, have reached at some aspect of performance, even more than metallocene catalyst, have become the Ziegler-that continues Olefin polymerization catalysis of new generation after Natta and metallocene catalyst.The difference of the central atom according to major catalyst, enters One step can divide into again mistake after non-metallocene (IIIB race, Group IVB, VB race, group vib, VIIB race) catalyst and non-cyclopentadienyl Cross metal (VIII) catalyst.By the function admirable of the polyolefin products manufactured by such catalyst, and low cost of manufacture. Non-metallocene catalyst coordination atom is oxygen, nitrogen, sulfur and phosphorus, does not contains cyclopentadienyl group or its deriveding group, such as indenyl and Fluorenyls etc., is characterized in that central ion has stronger electrophilicity, and have cis alkyl or halogen metal division center, easily Carry out alkene to insert and σ-key transfer, the easy alkylation of central metal, the beneficially generation at cation activity center；Formed Coordination compound has a geometric configuration of restriction, stereo selectivity, electronegativity and chirality controllability, it addition, the metal formed- Carbon bond easily polarizes, and is more beneficial for polymerization and the combined polymerization of alkene.Therefore, even if also can obtain under higher polymeric reaction temperature Obtain the olefin polymer of higher molecular weight.

But homogeneous catalyst has been found in olefinic polyreaction, and its active persistent period is short, easily glue still, height MAO consumption, and obtain that polymer molecular weight is the lowest or the most high weak point, be simply possible to use in polymerisation in solution work Skill or high-pressure polymerization process, seriously limit its industrial applicability.

Common practice is by certain supported technology by non-metallocene catalyst, makes loaded catalyst, from And improve the polymerization of alkene and the particle shape of resulting polymers.It shows as the most suitably reducing catalysis The initial activity of agent, extends the polymerization activity life-span of catalyst, reduces and even avoids the caking in polymerization process or sudden and violent poly-existing As, improve the form of polymer, improve the apparent density of polymer, it can be made to meet more polymerisation process, such as gas Phase-polymerization or slurry polymerization etc..

Chinese patent CN1539856A discloses the supported method of the non-metallocene catalyst of a kind of composite carrier load, It is characterized in that the method comprises the following steps: (1) using as the porosu solid of carrier at 100-1000 DEG C, inert atmosphere or subtract Under the conditions of pressure, it is dried or roasting 1 ~ 24h carries out thermal activation；(2) magnesium compound is dissolved in oxolane-ol mixed system Form solution, then the porosu solid of thermal activation is joined in this solution, under 0～60 DEG C of stirring condition, fully react formation Transparent system；Through filtration washing, it is dried and prepares complex carrier after draining；Or this transparent solvent is added nonpolar organic molten Agent is allowed to precipitate fully precipitation, then filtration washing, be dried and drain prepared complex carrier；(3) non-metallocene olefin polymerization is urged Agent is dissolved in solvent, then with complex carrier or modify washing and filtering after complex carrier contact 12～72 hours, dry take out Dry, become load type non-metallocene catalyst.From embodiment, catalyst is that activity is relatively low at catalysis in olefine polymerization.

Patent 200910180601.4 discloses the preparation method of a kind of load type non-metallocene catalyst, and it is to make magnesium Compound and Nonmetallocene coordination compound are dissolved in solvent, add and are dried after the porous carrier of thermal activation treatment, are loaded Type non-metallocene catalyst.Patent 200910180606.7 discloses the preparation method of a kind of load type non-metallocene catalyst, It is to make magnesium compound and Nonmetallocene coordination compound be dissolved in solvent, adds after the porous carrier of thermal activation treatment, then After adding precipitant, filtration washing is dried, and obtains load type non-metallocene catalyst.Both approaches all uses thermal activation The porous carrier processed, although porous carrier is through thermal activation treatment, dehydration and dehydroxylation, but still also has more amount on surface Free hydroxyl, follow-up load non-metallocene metal complex is had a negative impact, limits its activation plays.

Chinese patent 200910180100.6,200910180607.1,200910210988.3,200910210984.5, 200910210987.9, load type non-metallocene catalyst preparation method disclosed in 200910210991.5 and above-mentioned patent class Seemingly, all use porous carrier that thermal activation treatment crosses with containing Nonmetallocene part or the magnesium of Nonmetallocene coordination compound Polymer solution reacts, and reacts with the chemical treatments containing Group IVB metallic compound the most again, obtains load type non-metallocene catalysis Agent.

Chinese patent 200910180602.9 discloses the preparation method of a kind of load type non-metallocene catalyst, and it is to make Magnesium compound and Nonmetallocene coordination compound are dissolved in solvent, obtain load type non-metallocene catalyst after drying.Patent 200910180605.2 preparation methoies disclosing a kind of load type non-metallocene catalyst, it is to make magnesium compound and non-cyclopentadienyl gold Metal complex is dissolved in solvent, adds precipitant precipitation, and filtration washing obtains load type non-metallocene catalyst after drying.This Two kinds of methods use magnesium compound carrier, and the particle shape of catalyst is difficult to control to, and limit that thus polymerization obtains is poly- Polymer beads form.

Patent 200910180603.3,200910180604.8,200910210989.8,200910210986.4, 200910210985.X, load type non-metallocene catalyst preparation method disclosed in 200910210990.0 and above-mentioned patent class Seemingly, all using magnesium compound as carrier, the particle shape that still there is catalyst is difficult to control to, and limits and is thus polymerized The morphology obtained.

Therefore, current present situation is, is still required for a kind of load type non-metallocene catalyst, and its preparation method is simple, suitable Close industrialized production, and those problems present in prior art load type non-metallocene catalyst can be overcome.

Summary of the invention

The present inventor finds through diligent research on the basis of existing technology, by using the one specifically side of preparation Method manufactures described load type non-metallocene catalyst, it is possible to solves foregoing problems, and this completes the present invention.

In the preparation method of the load type non-metallocene catalyst of the present invention, without any proton (such as this area Conventional use of those).It addition, in the preparation method of the load type non-metallocene catalyst of the present invention, without to electronics Body (such as this area manufacture Ziegler or conventional use of monoesters class during Ziegler-Natta catalyst, di esters, two ethers, The compound such as diones and diol-lipid).Furthermore, in the preparation method of the load type non-metallocene catalyst of the present invention, also Need not harsh reaction requirement and reaction condition.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for Industrialized production.

Specifically, the present invention relates to the content of following aspect:

1. a preparation method for load type non-metallocene catalyst, comprises the following steps:

Magnesium compound and Nonmetallocene part is made to be dissolved in the presence of an alcohol in solvent, it is thus achieved that the step of magnesium compound solution Suddenly；

In described magnesium compound solution, add precipitant or be dried described magnesium compound solution, it is thus achieved that magnesium compound carries The step of body；

Make described magnesium compound carrier and the silicon compound of lower formula (X) and the chemical treatment selected from IV B race metallic compound Agent contacts, it is thus achieved that the step of described load type non-metallocene catalyst,

Si(OR)_mX_4-mFormula (X)

Wherein, each R is identical or different, is each independently selected from C_1-8Straight or branched alkyl, selects the most independently of one another From C_1-4Straight or branched alkyl, is preferably all ethyl；M is the integer of 0,1,2,3 or 4；Each X is identical or different, each independent Ground is selected from halogen, preferably chlorine,

Described preparation method is optionally additionally included in and makes at described magnesium compound carrier and described silicon compound and described chemistry Before reason agent contact, with helping magnesium compound described in chemical treatments pretreatment selected from aikyiaiurnirsoxan beta, alkyl aluminum or its combination in any The step of carrier.

According to the preparation method described in any preceding aspect, it is characterised in that described magnesium compound is selected from magnesium halide, alcoxyl One or more in base magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium, are preferably selected from halogenation One or more in magnesium, more preferably magnesium chloride.

According to the preparation method described in any preceding aspect, it is characterised in that described solvent is selected from C_6-12Aromatic hydrocarbon, halo C_6-12One or more in aromatic hydrocarbon, ester and ether, preferably C_6-12One or more in aromatic hydrocarbon and oxolane, most preferably Oxolane, one or more in fatty alcohol, aromatic alcohol and alicyclic ring alcohol of described alcohol, wherein said alcohol is optionally selected from halogen Atom or C_1-6The substituent group of alkoxyl replaces, and described alcohol is preferably selected from one or more in fatty alcohol, is more preferably selected from ethanol With one or more in butanol.

According to the preparation method described in any preceding aspect, it is characterised in that described Nonmetallocene part selected from have as One or more in the compound of lower chemical structural formula:

,

One or more in the compound (A) being preferably selected from there is following chemical structural formula and compound (B):

With,

(A) (B)

It is more preferably selected from the compound (A-1) with following chemical structural formula to compound (A-4) and compound (B-1) extremely One or more in compound (B-4):

、、

(A-1) (A-2)

、、

(A-3) (A-4)

、、

(B-1) (B-2)

With,

(B-3) (B-4)

In above all of chemical structural formula,

Q is 0 or 1；

D is 0 or 1；

A selected from oxygen atom, sulphur atom, selenium atom,、-NR²³R²⁴、-N(O)R²⁵R²⁶、、-PR²⁸R²⁹、-P(O) R³⁰OR³¹, sulfuryl, sulfoxide group or-Se (O) R³⁹, wherein N, O, S, Se and P respectively coordination atom；

B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C₁-C₃₀Alkyl；

D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C₁-C₃₀Alkyl, Sulfuryl, sulfoxide group,、-N(O)R²⁵R²⁶、Or-P (O) R³²(OR³³), wherein N, O, S, Se and P are respectively coordinated use Atom；

E selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se With P respectively coordination atom；

F selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P respectively coordination atom；

G is selected from C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or safing function group；

Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, rolls into a ball or phosphorus-containing groups containing seleno, and wherein N, O, S, Se and P are each From for coordination atom；

Z selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se With P respectively coordination atom；

Represent singly-bound or double bond；

Represent covalent bond or ionic bond；

R¹To R⁴、R⁶To R³⁶、R³⁸And R³⁹It is each independently selected from hydrogen, C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or lazy Sexual function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather Bonding or cyclization, be preferably formed as aromatic ring；

Described safing function group selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, containing sulfenyl Roll into a ball, containing tin group, C₁-C₁₀Ester group and nitro；

R⁵Lone pair electrons, hydrogen, C on nitrogen₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl, oxy radical, sulfur-containing group, Nitrogen-containing group, containing seleno group or phosphorus-containing groups；Work as R⁵For oxy radical, sulfur-containing group, nitrogen-containing group, roll into a ball or phosphorous-containigroups groups containing seleno During group, R⁵In N, O, S, P and Se can be coordinated as coordination atom and described center IV B race metallic atom；

Described substituted C₁-C₃₀Alkyl is selected from one or more halogens or C₁-C₃₀Alkyl alternatively base C₁-C₃₀Alkyl,

The described Nonmetallocene part further preferably one or many in the compound with following chemical structural formula Kind:

、、、、With,

Described Nonmetallocene part is most preferably selected from having one or more in the compound of following chemical structural formula:

With。

According to the preparation method described in any preceding aspect, it is characterised in that

Described halogen is selected from F, Cl, Br or I；

Described nitrogen-containing group is selected from、-NR²³R²⁴、-T-NR²³R²⁴Or-N (O) R²⁵R²⁶；

Described phosphorus-containing groups is selected from、-PR²⁸R²⁹、-P(O)R³⁰R³¹Or-P (O) R³²(OR³³)；

Described oxy radical is selected from hydroxyl ,-OR³⁴With-T-OR³⁴；

Described sulfur-containing group is selected from-SR³⁵、-T-SR³⁵、-S(O)R³⁶Or-T-SO₂R³⁷；

The described group containing seleno is selected from-SeR³⁸、-T-SeR³⁸、-Se(O)R³⁹Or-T-Se (O) R³⁹；

Described group T is selected from C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or safing function group；

Described R³⁷Selected from hydrogen, C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or safing function group；

Described C₁-C₃₀Alkyl is selected from C₁-C₃₀Alkyl, C₇-C₅₀Alkaryl, C₇-C₅₀Aralkyl, C₃-C₃₀Ring-type alkane Base, C₂-C₃₀Thiazolinyl, C₂-C₃₀Alkynyl, C₆-C₃₀Aryl, C₈-C₃₀Condensed ring radical or C₄-C₃₀Heterocyclic radical, wherein said heterocycle Base contains 1-3 selected from nitrogen-atoms, oxygen atom or the hetero atom of sulphur atom；

Described silicon-containing group is selected from-SiR⁴²R⁴³R⁴⁴Or-T-SiR⁴⁵；

Described germanic group is selected from-GeR⁴⁶R⁴⁷R⁴⁸Or-T-GeR⁴⁹；

Described containing tin group selected from-SnR⁵⁰R⁵¹R⁵²、-T-SnR⁵³Or-T-Sn (O) R⁵⁴；

Described R⁴²To R⁵⁴It is each independently selected from hydrogen, aforementioned C₁-C₃₀Alkyl, aforementioned substituted C₁-C₃₀Alkyl or aforementioned Safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can be bonded to each other one Play bonding or cyclization, and

Described group T is as previously defined.

According to the preparation method described in any preceding aspect, it is characterised in that the described magnesium compound in terms of Mg element with The mol ratio of described Nonmetallocene part is 1:0.0001-1, preferably 1:0.0002-0.4, more preferably 1:0.0008-0.2, enters one Walking preferred 1:0.001-0.1, described magnesium compound is 1mol:75～400ml with the ratio of described solvent, preferably 1mol:150～ The mol ratio of 300ml, more preferably 1mol:200～250ml, the described magnesium compound counted with Mg element and described alcohol is as 1:0.02 ～4.00, preferably 1:0.05～3.00, more preferably 1:0.10～2.50, described precipitant is 1 with the volume ratio of described solvent: 0.2～5, preferably 1:0.5～2, more preferably 1:0.8～1.5, the described magnesium compound carrier in terms of Mg element with in terms of Si element The mol ratio of described silicon compound be 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.05-0.25, in terms of Mg element Described magnesium compound carrier with the mol ratio of the described chemical treatments of Group IVB elemental metal as 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30, and the described magnesium compound carrier in terms of Mg element with in terms of Al element The described mol ratio helping chemical treatments is 1:0-1.0, preferably 1:0-0.5, more preferably 1:0.1-0.5.

According to the preparation method described in any preceding aspect, it is characterised in that described precipitant selected from alkane, cycloalkane, One or more in halogenated alkane and halo cycloalkane, are preferably selected from pentane, hexane, heptane, octane, nonane, decane, hexamethylene Alkane, Pentamethylene., cycloheptane, cyclodecane, cyclononane, dichloromethane, dichloro hexane, two chloroheptanes, chloroform, trichloroethane, Three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane, three n-butyl bromide, chlorocyclopentane, chlorine For hexamethylene, chloro cycloheptane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromine For one or more in cycloheptane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane, further preferably selected from hexane, One or more in heptane, decane and hexamethylene, most preferably hexane.

According to the preparation method described in any preceding aspect, it is characterised in that described IV B race metallic compound is selected from IV B Race's metal halide, IV B race metal alkyl compound, IV B race metal alkoxide, IV B race metal alkyl halides and One or more in IV B race metal alkoxide halogenide, are preferably selected from one or more in IV B race metal halide, more It is preferably selected from TiCl₄、TiBr₄、ZrCl₄、ZrBr₄、HfCl₄And HfBr₄In one or more, be most preferably selected from TiCl₄With ZrCl₄In one or more, described aikyiaiurnirsoxan beta is selected from MAO, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl One or more in aikyiaiurnirsoxan beta, are more preferably selected from one or more in MAO and isobutyl aluminium alkoxide, and described Alkyl aluminum selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminum, three positive penta One or more in base aluminum, three hexyl aluminum, three isohesyl aluminum, diethylmethyl aluminum and dimethyl ethyl aluminum, are preferably selected from three One or more in aluminium methyl, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, are most preferably selected from triethyl aluminum and three isobutyls One or more in base aluminum.

A kind of load type non-metallocene catalyst, it is to be manufactured by according to the preparation method described in any preceding aspect.

A kind of alkene homopolymerization/copolymerization method, it is characterised in that to be catalyzed according to the load type non-metallocene described in aspect 9 Agent is major catalyst, with the one in aikyiaiurnirsoxan beta, alkyl aluminum, haloalkyl aluminum, boron halothane, boron alkyl and boron alkyl ammonium salt Or multiple for promoter, make alkene homopolymerization or copolymerization.

11. 1 kinds of alkene homopolymerization/copolymerization methods, it is characterised in that comprise the following steps:

Load type non-metallocene catalyst is manufactured according to the preparation method described in any preceding aspect, and

With described load type non-metallocene catalyst as major catalyst, with selected from aikyiaiurnirsoxan beta, alkyl aluminum, haloalkyl aluminum, One or more in boron halothane, boron alkyl and boron alkyl ammonium salt are promoter, make alkene homopolymerization or copolymerization.

Technique effect

The preparation method technique simple possible of the load type non-metallocene catalyst of the present invention, adjustable leeway is big, can be effective Control active component content in catalyst, and then obtain the load type non-metallocene catalyst of different performance.

When the load type non-metallocene catalyst using the present invention to be obtained constitutes catalyst system and catalyzing with promoter, it is only necessary to Fewer promoter (such as MAO or triethyl aluminum) consumption, it is possible to obtain high olefin polymerizating activity, altogether Showing significant comonomer effect time poly-, i.e. under conditions of relatively equal, Copolymerization activity is higher than homopolymerization activity.

According to the present invention, the polyolefin (especially ethene polymers) obtained by alkene homopolymerization/copolymerization method Grain form is excellent, bulk density is high, narrow molecular weight distribution, the ultra-high molecular weight polyethylene molecule that in the presence of no hydrogen prepared by homopolymerization Measure higher and adjustable.

Detailed description of the invention

Below the detailed description of the invention of the present invention is described in detail, it should be noted however that the protection of the present invention Scope is the most limited to these specific embodiments, but is determined by claims of annex.

In the context of the present invention, unless otherwise defined explicitly, or this implication is beyond those skilled in the art's Understanding scope, hydrocarbon more than 3 carbon atoms or hydrocarbon derivative group (such as propyl group, propoxyl group, butyl, butane, butylene, butylene Base, hexane etc.) be respectively provided with not titled with prefix " just " time with titled with implication identical time prefix " just ".Such as, propyl group is typically managed Solving is n-pro-pyl, and butyl is generally understood as normal-butyl.

In this manual, in order to avoid statement complexity, not for each substituent group or group its valency clear and definite of compound Key-like condition be monovalence, bivalence, trivalent or tetravalence etc., those skilled in the art can be according to these substituent groups or group (ratio As described in this specification or definition group G, D, B, A and F etc.) location or institute on the structural formula of respective compound The replacement situation of performance specifically judges, and selects in these substituent groups or group given a definition that from this specification In the definition that the valence link situation of this position or the situation of replacement is suitable for.

The present invention relates to the preparation method of a kind of load type non-metallocene catalyst, comprise the following steps: make magnesium compound It is dissolved in the presence of an alcohol in solvent with Nonmetallocene part, it is thus achieved that the step of magnesium compound solution；To described magnesium compound Solution adds precipitant or is dried described magnesium compound solution, it is thus achieved that the step of magnesium compound carrier；With make described magnesium The silicon compound of compound carrier and formula (X) and the chemical treatments selected from IV B race metallic compound contact, it is thus achieved that described support type The step of non-metallocene catalyst.

Hereinafter the step obtaining described magnesium compound solution is specifically described.

According to this step, magnesium compound and Nonmetallocene part is made to be dissolved in suitable solvent in the presence of an alcohol (also referred to as For dissolving magnesium compound solvent) in, thus obtain described magnesium compound solution.

As described solvent, C such as can be enumerated_6-12Aromatic hydrocarbon, halo C_6-12Aromatic hydrocarbon, ester and ether equal solvent.Specifically than As can enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene, Ethyl acetate and oxolane etc..Wherein, preferably C_6-12Aromatic hydrocarbon and oxolane, most preferably oxolane.

These solvents can be used alone one, it is also possible to is used in mixed way so that arbitrary ratio is multiple.

According to the present invention, term " alcohol " refers to hydrocarbon chain (such as C_1-30Hydrocarbon) at least one hydrogen atom be optionally substituted by a hydroxyl group And the compound obtained.

As described alcohol, C such as can be enumerated_1-30Fatty alcohol (preferably C_1-30Aliphatic monobasic alcohol), C_6-30Aromatic alcohol is (excellent Select C_6-30Aromatic monoalcohols) and C_4-30Alicyclic ring alcohol (preferably C_4-30Alicyclic monohydric alcohol), wherein preferably C_1-30Aliphatic monobasic alcohol Or C_2-8Aliphatic monobasic alcohol, more preferably ethanol and butanol.It addition, described alcohol can optionally be selected from halogen atom or C_1-6Alkoxyl Substituent group replace.

As described C_1-30Fatty alcohol, such as can enumerate methanol, ethanol, propanol, 2-propanol, butanol, amylalcohol, 2-methyl Amylalcohol, 2-ethylpentanol, 2-hexyl butanol, hexanol and 2-Ethylhexyl Alcohol etc., wherein preferred alcohol, butanol and 2-Ethylhexyl Alcohol.

As described C_6-30Aromatic alcohol, such as can enumerate benzyl alcohol, phenethanol and methylbenzyl alcohol etc., wherein preferred benzene Ethanol.

As described C_4-30Alicyclic ring alcohol, such as can enumerate Hexalin, cyclopentanol, Lotka-Volterra circle system, methylcyclopentanol, ethyl ring Amylalcohol, propyl group cyclopentanol, methyl cyclohexanol, ethyl cyclohexanol, cyclohexyl alcohol, methyl Lotka-Volterra circle system, ethyl Lotka-Volterra circle system and propyl group Lotka-Volterra circle system etc., wherein preferred Hexalin and methyl cyclohexanol.

As the described alcohol replaced by halogen atom, trichlorine methanol, ethapon and three Mecorals etc. such as can be enumerated, its In preferred trichlorine methanol.

As the described alcohol replaced by alkoxyl, glycol-ether, ethylene glycol-n-butyl ether and 1-fourth such as can be enumerated Epoxide-2-propanol etc., wherein preferred glycol-ether.

These alcohol can be used alone one, it is also possible to multiple is used in mixed way.When using with the form of multiple mixing, institute The ratio stated between any two kinds of alcohol in alcohol mixture can arbitrarily determine, and is not particularly limited.

In order to prepare described magnesium compound solution, described magnesium compound and described Nonmetallocene part can be added to by The mixed solvent that described solvent and described alcohol are formed dissolves, or by described magnesium compound and described Nonmetallocene part Add in described solvent, and subsequently or simultaneously interpolation alcohol dissolves, but be not limited to this.

To the preparation time of described magnesium compound solution (during the dissolving of the most described magnesium compound and described Nonmetallocene part Between) there is no particular limitation, but generally 0.5～24h, preferably 4～24h.In this preparation process, it is possible to use stirring promotees Enter described magnesium compound and the dissolving of described Nonmetallocene part.This stirring can use any form, such as stirring paddle (rotating speed Generally 10～1000 revs/min) etc..As required, sometimes can promote to dissolve by suitable heating.

Hereinafter described magnesium compound is specifically described.

According to the present invention, term " magnesium compound " uses the common concept in this area, refers to gather as load-type alkene Close the carrier conventional use of organic or inorganic solid water-free magnesium-containing compound of catalyst.

According to the present invention, as described magnesium compound, such as can enumerate magnesium halide, Alkoxymagnesium halides, alkoxyl magnesium, Alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium.

Specifically, as described magnesium halide, magnesium chloride (MgCl such as can be enumerated₂), magnesium bromide (MgBr₂), magnesium iodide (MgI₂) and Afluon (Asta) (MgF₂) etc., wherein preferred magnesium chloride.

As described Alkoxymagnesium halides, methoxy magnesium chloride (Mg (OCH such as can be enumerated₃) Cl), ethyoxyl chlorination Magnesium (Mg (OC₂H₅) Cl), propoxyl group magnesium chloride (Mg (OC₃H₇) Cl), n-butoxy magnesium chloride (Mg (OC₄H₉) Cl), isobutoxy Magnesium chloride (Mg (i-OC₄H₉) Cl), methoxyl group magnesium bromide (Mg (OCH₃) Br), ethyoxyl magnesium bromide (Mg (OC₂H₅) Br), propoxyl group Magnesium bromide (Mg (OC₃H₇) Br), n-butoxy magnesium bromide (Mg (OC₄H₉) Br), isobutoxy magnesium bromide (Mg (i-OC₄H₉) Br), Methoxyl group magnesium iodide (Mg (OCH₃) I), ethyoxyl magnesium iodide (Mg (OC₂H₅) I), propoxyl group magnesium iodide (Mg (OC₃H₇) I), positive fourth Epoxide magnesium iodide (Mg (OC₄H₉) I) and isobutoxy magnesium iodide (Mg (i-OC₄H₉) I) etc., wherein preferred methoxy magnesium chloride, second Epoxide magnesium chloride and isobutoxy magnesium chloride.

As described alkoxyl magnesium, magnesium methoxide (Mg (OCH such as can be enumerated₃)₂), magnesium ethylate (Mg (OC₂H₅)₂), Propoxyl group magnesium (Mg (OC₃H₇)₂), butoxy magnesium (Mg (OC₄H₉)₂), isobutoxy magnesium (Mg (i-OC₄H₉)₂) and 2-ethyl hexyl oxy Magnesium (Mg (OCH₂CH(C₂H₅)C₄H)₂) etc., wherein preferred magnesium ethylate and isobutoxy magnesium.

As described alkyl magnesium, methyl magnesium (Mg (CH such as can be enumerated₃)₂), magnesium ethide (Mg (C₂H₅)₂), propyl group magnesium (Mg (C₃H₇)₂), normal-butyl magnesium (Mg (C₄H₉)₂) and isobutyl group magnesium (Mg (i-C₄H₉)₂) etc., wherein preferred magnesium ethide and normal-butyl magnesium.

As described alkyl halide magnesium, methyl-magnesium-chloride (Mg (CH such as can be enumerated₃) Cl), ethylmagnesium chloride (Mg (C₂H₅) Cl), propyl group magnesium chloride (Mg (C₃H₇) Cl), n-butylmagnesium chloride magnesium (Mg (C₄H₉) Cl), isobutyl group magnesium chloride (Mg (i- C₄H₉) Cl), methyl-magnesium-bromide (Mg (CH₃) Br), ethylmagnesium bromide (Mg (C₂H₅) Br), propyl group magnesium bromide (Mg (C₃H₇) Br), just Butyl magnesium bromide (Mg (C₄H₉) Br), selenium alkynide (Mg (i-C₄H₉) Br), methylpyridinium iodide magnesium (Mg (CH₃) I), ethyl phosphonium iodide Magnesium (Mg (C₂H₅) I), propyl group magnesium iodide (Mg (C₃H₇) I), normal-butyl magnesium iodide (Mg (C₄H₉) I) and isobutyl group magnesium iodide (Mg (i- C₄H₉) I) etc., wherein preferred methyl-magnesium-chloride, ethylmagnesium chloride and isobutyl group magnesium chloride.

As described alkyl alkoxy magnesium, methyl methoxy base magnesium (Mg (OCH such as can be enumerated₃)(CH₃)), methylethoxy Base magnesium (Mg (OC₂H₅)(CH₃)), methyl-prop epoxide magnesium (Mg (OC₃H₇)(CH₃)), methyl n-butoxy magnesium (Mg (OC₄H₉) (CH₃)), methyl tert-butyl epoxide magnesium (Mg (i-OC₄H₉)(CH₃)), ethyl magnesium methoxide (Mg (OCH₃)(C₂H₅)), ethyl ethyoxyl Magnesium (Mg (OC₂H₅)(C₂H₅)), ethylpropoxy magnesium (Mg (OC₃H₇)(C₂H₅)), ethyl n-butoxy magnesium (Mg (OC₄H₉) (C₂H₅)), ethyl isobutyl epoxide magnesium (Mg (i-OC₄H₉)(C₂H₅)), propylmethoxy magnesium (Mg (OCH₃)(C₃H₇)), propyl group ethoxy Base magnesium (Mg (OC₂H₅)(C₃H₇)), propyl group propoxyl group magnesium (Mg (OC₃H₇)(C₃H₇)), propyl group n-butoxy magnesium (Mg (OC₄H₉) (C₃H₇)), propyl group isobutoxy magnesium (Mg (i-OC₄H₉)(C₃H₇)), normal-butyl magnesium methoxide (Mg (OCH₃)(C₄H₉)), normal-butyl Magnesium ethylate (Mg (OC₂H₅)(C₄H₉)), normal-butyl propoxyl group magnesium (Mg (OC₃H₇)(C₄H₉)), normal-butyl n-butoxy magnesium (Mg (OC₄H₉)(C₄H₉)), normal-butyl isobutoxy magnesium (Mg (i-OC₄H₉)(C₄H₉)), isobutyl group magnesium methoxide (Mg (OCH₃)(i- C₄H₉)), isobutyl group magnesium ethylate (Mg (OC₂H₅) (i-C₄H₉)), isobutyl group propoxyl group magnesium (Mg (OC₃H₇) (i-C₄H₉)), different Butyl n-butoxy magnesium (Mg (OC₄H₉) (i-C₄H₉)) and isobutyl group isobutoxy magnesium (Mg (i-OC₄H₉) (i-C₄H₉)) etc., its In preferred butyl magnesium ethylate.

These magnesium compounds can be used alone one, it is also possible to multiple is used in mixed way, and is not particularly limited.

When using with the form of multiple mixing, between two kinds of magnesium compounds in described magnesium compound mixture mole It is frequently such as 0.25～4:1, preferably 0.5～3:1, more preferably 1～2:1.

According to the present invention, term " Nonmetallocene coordination compound " is a kind of single centre alkene for metallocene catalyst Polymerized hydrocarbon catalyst, does not contains the cyclopentadienyl group or derivatives thereofs such as cyclopentadienyl ring, fluorenes ring or indenes ring in structure, and with co-catalysis Metallo-organic compound (the therefore institute of olefinic polymerization catalysis activity is can show that during agent (such as those described below) combination State Nonmetallocene coordination compound and be also sometimes referred to as non-metallocene olefin polymerization coordination compound).It is former that this compound comprises central metal Son and at least one multidentate ligand being combined with coordinate bond with described central metal atom (preferably tridentate ligand or more multiple tooth join Body), and term " Nonmetallocene part " is aforesaid multidentate ligand.

According to the present invention, described Nonmetallocene part is selected from the compound with following chemical structural formula:

。

According to the present invention, group A, D and E(coordination group in this compound) by its contained coordination atom Contained by the IV B race metallic compound used as chemical treatments in hetero atoms such as () such as N, O, S, Se and P and the present invention The metallic atom generation complexation reaction of IV B race and form coordinate bond, be consequently formed metallic atom centered by this IV B race metallic atom Coordination compound (Nonmetallocene coordination compound the most of the present invention).

In one more specifically embodiment, described Nonmetallocene part is selected from the change with following chemical structural formula Compound (A) and compound (B):

With。

(A) (B)

In one more specifically embodiment, described Nonmetallocene part is selected from the change with following chemical structural formula Compound (A-1) is to compound (A-4) and compound (B-1) to compound (B-4):

、、

(A-1) (A-2)

、、

(A-3) (A-4)

、、

(B-1) (B-2)

With。

(B-3) (B-4)

In all above chemical structural formula,

Q is 0 or 1；

D is 0 or 1；

A selected from oxygen atom, sulphur atom, selenium atom,、-NR²³R²⁴、-N(O)R²⁵R²⁶、、-PR²⁸R²⁹、-P(O) R³⁰OR³¹, sulfuryl, sulfoxide group or-Se (O) R³⁹, wherein N, O, S, Se and P respectively coordination atom；

B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C₁-C₃₀Alkyl；

D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C₁-C₃₀Alkyl, Sulfuryl, sulfoxide group,、-N(O)R²⁵R²⁶、Or-P (O) R³²(OR³³), wherein N, O, S, Se and P are respectively coordination with former Son；

E selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group (-CN), wherein N, O, S, Se and P respectively coordination atom；

F selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P respectively coordination atom；

G is selected from C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or safing function group；

Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, rolls into a ball or phosphorus-containing groups containing seleno, and wherein N, O, S, Se and P are each From for coordination atom；

Z selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group (-CN), the most permissible Enumerate-NR²³R²⁴、-N(O)R²⁵R²⁶、-PR²⁸R²⁹、-P(O)R³⁰R³¹、-OR³⁴、-SR³⁵、-S(O)R³⁶、-SeR³⁸Or-Se (O) R³⁹, Wherein N, O, S, Se and P respectively coordination atom；

Represent singly-bound or double bond；

Represent covalent bond or ionic bond.

R¹To R⁴、R⁶To R³⁶、R³⁸And R³⁹It is each independently selected from hydrogen, C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl is (wherein Preferably halohydrocarbyl, such as-CH₂Cl and-CH₂CH₂Or safing function group Cl).Above-mentioned group can identical also may be used to each other With difference, wherein adjacent group such as R¹With R², R⁶With R⁷, R⁷With R⁸, R⁸With R⁹, R¹³With R¹⁴, R¹⁴With R¹⁵, R¹⁵With R¹⁶, R¹⁸With R¹⁹, R¹⁹With R²⁰, R²⁰With R²¹, R²³With R²⁴, or R²⁵With R²⁶Etc. can combine togather bonding or cyclization, it is preferably formed as Aromatic ring, the most unsubstituted phenyl ring or by 1-4 C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl (wherein preferred halogenated hydrocarbons Base, such as-CH₂Cl and-CH₂CH₂Or the substituted phenyl ring of safing function group Cl).

R⁵Lone pair electrons, hydrogen, C on nitrogen₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl, oxy radical, sulfur-containing group, Nitrogen-containing group, containing seleno group or phosphorus-containing groups.Work as R⁵For oxy radical, sulfur-containing group, nitrogen-containing group, roll into a ball or phosphorous-containigroups groups containing seleno During group, R⁵In N, O, S, P and Se can be coordinated as coordination atom and described center IV B race metallic atom.

In the context of the present invention, described safing function group such as can be enumerated selected from halogen, oxy radical, contain Nitrogen groups, silicon-containing group, germanic group, sulfur-containing group, containing tin group, C₁-C₁₀Ester group or nitro (-NO₂) at least one Deng, but generally do not include C₁-C₃₀Alkyl and substituted C₁-C₃₀Alkyl.

In the context of the present invention, limited by the chemical constitution of multidentate ligand of the present invention, described safing function Group has the following characteristics that

(1) complexation process of described group A, D, E, F, Y or Z and described central metal atom M is not disturbed, and

(2) coordination ability with described central metal atom M is less than described A, D, E, F, Y and Z group, and does not replace this A little groups and the coordination of described central metal atom M.

According to the present invention, in aforementioned all of chemical structural formula, as the case may be, any adjacent two or more Group, such as R²¹With group Z, or R¹³With group Y, can combine togather cyclization, is preferably formed as comprising and comes from institute State the heteroatomic C of group Z or Y₆-C₃₀Heteroaromatic, such as pyridine ring etc., wherein said heteroaromatic is optionally by 1 Or it is multiple selected from C₁-C₃₀Alkyl, substituted C₁-C₃₀The substituent group of alkyl and safing function group replaces.

In the context of the present invention,

Described halogen is selected from F, Cl, Br or I.Described nitrogen-containing group is selected from、-NR²³R²⁴、-T-NR²³R²⁴Or-N (O) R²⁵R²⁶.Described phosphorus-containing groups is selected from、-PR²⁸R²⁹、-P(O)R³⁰R³¹Or-P (O) R³²(OR³³).Described oxy radical is selected from Hydroxyl ,-OR³⁴With-T-OR³⁴.Described sulfur-containing group is selected from-SR³⁵、-T-SR³⁵、-S(O)R³⁶Or-T-SO₂R³⁷.Described containing seleno Group is selected from-SeR³⁸、-T-SeR³⁸、-Se(O)R³⁹Or-T-Se (O) R³⁹.Described group T is selected from C₁-C₃₀Alkyl, substituted C₁- C₃₀Alkyl or safing function group.Described R³⁷Selected from hydrogen, C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or safing function Group.

In the context of the present invention, described C₁-C₃₀Alkyl is selected from C₁-C₃₀Alkyl (preferably C₁-C₆Alkyl, the most different Butyl), C₇-C₅₀Alkaryl (such as tolyl, xylyl, diisobutyl phenyl etc.), C₇-C₅₀Aralkyl (such as benzyl Base), C₃-C₃₀Cyclic alkyl, C₂-C₃₀Thiazolinyl, C₂-C₃₀Alkynyl, C₆-C₃₀Aryl (such as phenyl, naphthyl, anthryl etc.), C₈-C₃₀Condensed ring radical or C₄-C₃₀Heterocyclic radical, wherein said heterocyclic radical contains 1-3 selected from nitrogen-atoms, oxygen atom or sulphur atom Hetero atom, such as pyridine radicals, pyrrole radicals, furyl or thienyl etc..

According to the present invention, in the context of the present invention, according to the concrete condition of the relevant group combined to it, described C₁-C₃₀Alkyl is sometimes referred to as C₁-C₃₀Hydrocarbon diyl (divalent group, or referred to as C₁-C₃₀Alkylene) or C₁-C₃₀Hydrocarbon three base (trivalent radical), this is obvious to those skilled in the art.

In the context of the present invention, described substituted C₁-C₃₀Alkyl refers to one or more inert substituents C₁-C₃₀Alkyl.So-called inert substituent, refer to these substituent groups to aforementioned coordinative group (refer to aforementioned group A, D, E, F, Y and Z, or the most optionally include R⁵) the most real with the complexation process of central metal atom (aforementioned IV B race metallic atom) The interference of matter；In other words, being limited by the chemical constitution of part of the present invention, these substituent groups have no ability to or have no chance (such as being affected by steric hindrance etc.) and the metallic atom generation complexation reaction of described IV B race and form coordinate bond.It is said that in general, institute State inert substituent selected from halogen or C₁-C₃₀Alkyl (preferably C₁-C₆Alkyl, such as isobutyl group).

In the context of the present invention, described silicon-containing group is selected from-SiR⁴²R⁴³R⁴⁴Or-T-SiR⁴⁵；Described germanic group selects From-GeR⁴⁶R⁴⁷R⁴⁸Or-T-GeR⁴⁹；Described containing tin group selected from-SnR⁵⁰R⁵¹R⁵²、-T-SnR⁵³Or-T-Sn (O) R⁵⁴；And institute State R⁴²To R⁵⁴It is each independently selected from hydrogen, aforesaid C₁-C₃₀Alkyl, aforesaid substituted C₁-C₃₀Alkyl or aforesaid inertia Functional groups, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into Key or cyclization.Wherein group T's is as defined above.

As described Nonmetallocene part, following compound such as can be enumerated:

、 、

、 、

、 、

、 、

、、

、 、

、 、

、 、

、、

、 、

、 、

、、

、 、

、 、

、 、

With。

Described Nonmetallocene part is preferably selected from following compound:

、、

、、

、 、

、 、

、 With

。

Described Nonmetallocene part is further preferably selected from following compound:

、、、、With。

Described Nonmetallocene part is more preferably selected from following compound:

With。

These Nonmetallocene parts can be used alone one, or is applied in combination multiple with arbitrary ratio.

According to the present invention, described Nonmetallocene part is not normally used as electronic donor compound capable in this area Diether compounds.

Described Nonmetallocene part can manufacture according to any method well known by persons skilled in the art.Make about it Make the particular content of method, such as can be found in WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 Deng, this specification introduces the full text of these documents as reference with regard to this.

According to the present invention, by described magnesium compound solution convection drying, it is possible to obtain consolidating of a kind of good fluidity The magnesium compound carrier of body product, the i.e. present invention.

Now, described convection drying can use conventional method to carry out, dry, vacuum atmosphere under such as inert gas atmosphere Lower it is dried or heat drying etc. under vacuum atmosphere, wherein preferred heat drying under vacuum atmosphere.Baking temperature is generally 30 ~ 160 DEG C, preferably 60 ~ 130 DEG C, it is generally 2～24h drying time, but is sometimes not limited to this.

Or, according to the present invention, add precipitant by metering in described magnesium compound solution, make solid matter from this Magnesium compound solution is precipitated out, is derived from magnesium compound carrier.

Hereinafter described precipitant is specifically described.

According to the present invention, term " precipitant " uses the common concept in this area, refers to reduce solid content solute (than magnesium compound, porous carrier, Nonmetallocene part or Nonmetallocene coordination compound etc. as mentioned) dissolving in its solution Degree also and then makes its chemical inertness liquid separated out in solid form from described solution.

According to the present invention, as described precipitant, such as can enumerate for solid content solute to be precipitated (such as described Magnesium compound, porous carrier, Nonmetallocene part or Nonmetallocene coordination compound etc.) for be poor solvent, and for being used for It is the solvent of good solvent for dissolving the described solvent of described solid content solute (such as magnesium compound), such as can enumerate C_5-12 Alkane, C_5-12Cycloalkane, halo C_1-10Alkane and halo C_5-12Cycloalkane.

As described C_5-12Alkane, such as can enumerate pentane, hexane, heptane, octane, nonane and decane etc., Qi Zhongyou Select hexane, heptane and decane, most preferably hexane.

As described C_5-12Cycloalkane, such as can enumerate hexamethylene, Pentamethylene., cycloheptane, cyclodecane and cyclononane etc., Most preferably hexamethylene.

As described halo C_1-10Alkane, such as can enumerate dichloromethane, dichloro hexane, two chloroheptanes, chloroform, Trichloroethane, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane and three n-butyl bromide etc..

As described halo C_5-12Cycloalkane, such as can enumerate chlorocyclopentane, chlorocyclohexane, chloro cycloheptane, Chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo cycloheptane, bromo cyclooctane, Bromo cyclononane and bromo cyclodecane etc..

These precipitant can be used alone one, it is also possible to is used in mixed way so that arbitrary ratio is multiple.

The feed postition of precipitant can be disposable addition or dropping, the most disposably adds.In this precipitation process In, it is possible to use stirring promotes the dispersion of precipitant, and beneficially the final of solid product precipitates.This stirring can use any Form (such as stirring paddle), and rotating speed is generally 10～1000 revs/min etc..

To the consumption of described precipitant, there is no particular limitation, but general the most by volume, described precipitant be used for dissolving The ratio of the described solvent of described magnesium compound is 1:0.2～5, preferably 1:0.5～2, more preferably 1:0.8～1.5.

To the temperature of described precipitant, also there is no particular limitation, but generally preferably room temperature is to being less than used any molten The temperature (preferably 20-80 DEG C, more preferably 40-60 DEG C) of the boiling point of agent and precipitant, but sometimes it is not limited to this.And, this sinks Shallow lake process general it is also preferred that room temperature to the boiling point being less than any solvent and the precipitant used temperature (preferably 20-80 DEG C, More preferably 40-60 DEG C) under carry out 0.3-12 hour, but be sometimes not limited to this, and be substantially completely precipitated as with solid product Accurate.

Completely after precipitation, the solid product obtained is filtered, washed and dried.For described filtration, washing and The method being dried is not particularly limited, and can use commonly used in the art those as required.

As required, described washing typically carries out 1 ~ 6 time, preferably 3 ~ 4 times.Wherein, washer solvent is preferably used with heavy The solvent that shallow lake agent is identical but it also may different.

Described being dried can use conventional method to carry out, under such as noble gas seasoning, boulton process or vacuum Heat drying method, preferably noble gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum seasoning.

Described dry temperature range is generally room temperature to 140 DEG C.It is generally drying time 2-20 hour, but can also Different according to the specifically used solvent case being used for dissolving described magnesium compound.Such as, oxolane conduct is being used When the solvent dissolving described magnesium compound, baking temperature is generally about 80 DEG C, is dried under vacuum 2 ~ 12 hours, And at employing toluene as during for dissolving the solvent of described magnesium compound, baking temperature is generally about 100 DEG C, under vacuo It is dried 4 ~ 24 hours.

According to the present invention, by the silicon compound of the magnesium compound carrier Yu formula (X) that make aforementioned acquisition with selected from IV B race gold Belong to the chemical treatments contact of compound, be derived from the load type non-metallocene catalyst of the present invention.

According to the present invention, by making described chemical treatments react with described magnesium compound carrier, cause at described chemistry The aforementioned Nonmetallocene part generation complexation reaction that reason agent is contained with on this magnesium compound carrier, thus at this magnesium compound carrier The Nonmetallocene coordination compound (the most supported reaction) of upper in-situ preparation metallic atom centered by described Group IVB metallic atom, This is a big feature of the present invention.

Hereinafter the silicon compound of described formula (X) is specifically described.

Si(OR)_mX_4-mFormula (X)

Wherein, each R is identical or different, is each independently selected from C_1-8Straight or branched alkyl, as methyl, ethyl, positive third Base, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, different pungent Base etc.；

M is the integer of 0,1,2,3 or 4；

Each X is identical or different, is each independently selected from halogen.

According to the present invention, as described halogen, fluorine, chlorine, bromine and iodine, wherein preferred chlorine such as can be enumerated.

According to the present invention, each R is the most identical or different, is each independently selected from C_1-4Straight or branched alkyl, the most all For ethyl.

As the silicon compound of described formula (X), can enumerate but be not limited to compound in detail below:

Tetramethoxy-silicane, tetraethoxy-silicane, four positive propoxy silicon, tetraisopropoxide silicon, four n-butoxy silicon, four isobutyl oxygen Base silicon, four n-pentyloxy silicon, tetraisoamoxy-silicane, four n-octyloxy silicon, four different octyloxy silicon, a methoxyl group triethoxysilicane, Dimethoxy diethoxy silicon, trimethoxy one ethyoxyl silicon, a methoxyl group three n-pro-pyl epoxide silicon, positive third oxygen of dimethoxy two Base silicon, trimethoxy one positive propoxy silicon, a methoxyl group triisopropyl epoxide silicon, dimethoxy diisopropoxy silicon, trimethoxy Base one isopropoxy silicon, a methoxyl group three normal-butyl epoxide silicon, dimethoxy two n-butoxy silicon, trimethoxy one n-butoxy Silicon, a methoxyl group triisobutyl epoxide silicon, dimethoxy two isobutoxy silicon, trimethoxy one isobutoxy silicon, an ethyoxyl Three n-pro-pyl epoxide silicon, diethoxy two positive propoxy silicon, triethoxy one positive propoxy silicon, an ethyoxyl triisopropyl epoxide Silicon, diethoxy diisopropoxy silicon, triethoxy one isopropoxy silicon, an ethyoxyl three normal-butyl epoxide silicon, diethoxy Two n-butoxy silicon, triethoxy one n-butoxy silicon, an ethyoxyl triisobutyl epoxide silicon, diethoxy two isobutoxy Four C such as silicon, triethoxy one isobutoxy silicon_1-8Straight or branched alkoxyl silicone, wherein preferred tetramethoxy-silicane, tetraethoxy Silicon, tetraisobutoxy-silicane, more preferably tetraethoxy-silicane；

Trimethoxy chloro silicon, dimethoxy chloro silicon, a methoxyl group chloro silicon, triethoxy chloro silicon, diethoxy Chloro silicon, an ethyoxyl chloro silicon, three isobutoxy chloro silicon, two isobutoxy chloro silicon, an isobutoxy chloro silicon, front three Epoxide bromo silicon, dimethoxy bromo silicon, a methoxyl group bromo silicon, triethoxy bromo silicon, diethoxy bromo silicon, an ethoxy Bromide is for C such as silicon, three isobutoxy bromo silicon, two isobutoxy bromo silicon, isobutoxy bromo silicon_1-8Straight or branched alkane Epoxide halo silicon, wherein preferred trimethoxy chloro silicon, dimethoxy chloro silicon, triethoxy chloro silicon, diethoxy chloro Silicon, more preferably triethoxy chloro silicon；

Silicon fluoride., Silicon chloride., Silicon bromide., silicon tetraiodide, the silicon tetrahalogen such as tribromo silicon chloride, trichlorine silicon bromide, Wherein preferred Silicon chloride..

These silicon compounds can be used alone one, or is applied in combination multiple with arbitrary ratio.

Hereinafter described chemical treatments is specifically described.

According to the present invention, using Group IVB metallic compound as described chemical treatments.

As described Group IVB metallic compound, such as can enumerate selected from Group IVB metal halide, Group IVB metal alkyl Compound, Group IVB metal alkoxide, Group IVB metal alkyl halides and Group IVB metal alkoxide halogenide are at least A kind of.

As described Group IVB metal halide, described Group IVB metal alkyl compound, described Group IVB metal alkoxide Compound, described Group IVB metal alkyl halides and described Group IVB metal alkoxide halogenide, such as can enumerate below formula The compound of structure:

M(OR¹)_mX_nR² _4-m-n

Wherein:

M is 0,1,2,3 or 4；

N is 0,1,2,3 or 4；

M is Group IVB metal in the periodic table of elements, such as titanium, zirconium and hafnium etc.；

X is halogen, such as F, Cl, Br and I etc.；And

R¹And R²It is each independently selected from C₁-₁₀Alkyl, such as methyl, ethyl, propyl group, normal-butyl, isobutyl group etc., R¹And R² Can be identical, it is also possible to different.

Specifically, as described Group IVB metal halide, titanium tetrafluoride (TiF such as can be enumerated₄), titanium tetrachloride (TiCl₄), titanium tetrabromide (TiBr₄), titanium tetra iodide (TiI₄)；

Zirconium tetrafluoride (ZrF₄), Zirconium tetrachloride. (ZrCl₄), tetrabormated zirconium (ZrBr₄), zirconium tetraiodide (ZrI₄)；

Tetrafluoride hafnium (HfF₄), hafnium tetrachloride (HfCl₄), hafnium (HfBr₄), tetraiodide hafnium (HfI₄).

As described Group IVB metal alkyl compound, tetramethyl titanium (Ti (CH such as can be enumerated₃)₄), tetraethyl titanium (Ti (CH₃CH₂)₄), four isobutyl group titanium (Ti (i-C₄H₉)₄), tetra-n-butyl titanium (Ti (C₄H₉)₄), triethyl methyl titanium (Ti (CH₃) (CH₃CH₂)₃), diethyl-dimethyl titanium (Ti (CH₃)₂(CH₃CH₂)₂), trimethylethyl titanium (Ti (CH₃)₃(CH₃CH₂)), three different Butyl methyl titanium (Ti (CH₃)(i-C₄H₉)₃), diisobutyl dimethyl titanium (Ti (CH₃)₂(i-C₄H₉)₂), trimethyl isobutyl group titanium (Ti (CH₃)₃(i-C₄H₉)), triisobutyl ethyl titanium (Ti (CH₃CH₂)(i-C₄H₉)₃), diisobutyl diethyl titanium (Ti (CH₃CH₂)₂(i-C₄H₉)₂), triethyl group isobutyl group titanium (Ti (CH₃CH₂)₃(i-C₄H₉)), three normal-butyl methyltitanium (Ti (CH₃) (C₄H₉)₃), di-n-butyl dimethyl titanium (Ti (CH₃)₂(C₄H₉)₂), trimethyl normal-butyl titanium (Ti (CH₃)₃(C₄H₉)), three positive fourths Ylmethyl titanium (Ti (CH₃CH₂)(C₄H₉)₃), di-n-butyl diethyl titanium (Ti (CH₃CH₂)₂(C₄H₉)₂), triethyl group normal-butyl titanium (Ti (CH₃CH₂)₃(C₄H₉)) etc.；

Tetramethyl zirconium (Zr (CH₃)₄), tetraethyl zirconium (Zr (CH₃CH₂)₄), four isobutyl group zirconium (Zr (i-C₄H₉)₄), four positive fourths Base zirconium (Zr (C₄H₉)₄), triethyl methyl zirconium (Zr (CH₃)(CH₃CH₂)₃), diethyl-dimethyl zirconium (Zr (CH₃)₂(CH₃CH₂)₂), Trimethylethyl zirconium (Zr (CH₃)₃(CH₃CH₂)), triisobutyl methylcyclopentadienyl zirconium (Zr (CH₃)(i-C₄H₉)₃), diisobutyl zirconium dimethyl (Zr (CH₃)₂(i-C₄H₉)₂), trimethyl isobutyl group zirconium (Zr (CH₃)₃(i-C₄H₉)), triisobutyl ethyl zirconium (Zr (CH₃CH₂)(i- C₄H₉)₃), diisobutyl diethyl zirconium (Zr (CH₃CH₂)₂(i-C₄H₉)₂), triethyl group isobutyl group zirconium (Zr (CH₃CH₂)₃(i- C₄H₉)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH₃)(C₄H₉)₃), di-n-butyl zirconium dimethyl (Zr (CH₃)₂(C₄H₉)₂), trimethyl just Butyl zirconium (Zr (CH₃)₃(C₄H₉)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH₃CH₂)(C₄H₉)₃), di-n-butyl diethyl zirconium (Zr (CH₃CH₂)₂(C₄H₉)₂), triethyl group normal-butyl zirconium (Zr (CH₃CH₂)₃(C₄H₉)) etc.；

Tetramethyl hafnium (Hf (CH₃)₄), tetraethyl hafnium (Hf (CH₃CH₂)₄), four isobutyl group hafnium (Hf (i-C₄H₉)₄), four positive fourths Base hafnium (Hf (C₄H₉)₄), triethyl methyl hafnium (Hf (CH₃)(CH₃CH₂)₃), diethyl-dimethyl hafnium (Hf (CH₃)₂(CH₃CH₂)₂), Trimethylethyl hafnium (Hf (CH₃)₃(CH₃CH₂)), triisobutyl methylcyclopentadienyl hafnium (Hf (CH₃)(i-C₄H₉)₃), diisobutyl dimethyl hafnium (Hf (CH₃)₂(i-C₄H₉)₂), trimethyl isobutyl group hafnium (Hf (CH₃)₃(i-C₄H₉)), triisobutyl ethyl hafnium (Hf (CH₃CH₂)(i- C₄H₉)₃), diisobutyl diethyl hafnium (Hf (CH₃CH₂)₂(i-C₄H₉)₂), triethyl group isobutyl group hafnium (Hf (CH₃CH₂)₃(i- C₄H₉)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH₃)(C₄H₉)₃), di-n-butyl dimethyl hafnium (Hf (CH₃)₂(C₄H₉)₂), trimethyl just Butyl hafnium (Hf (CH₃)₃(C₄H₉)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH₃CH₂)(C₄H₉)₃), di-n-butyl diethyl hafnium (Hf (CH₃CH₂)₂(C₄H₉)₂), triethyl group normal-butyl hafnium (Hf (CH₃CH₂)₃(C₄H₉)) etc..

As described Group IVB metal alkoxide, titanium tetramethoxide (Ti (OCH such as can be enumerated₃)₄), four ethoxies Base titanium (Ti (OCH₃CH₂)₄), four isobutoxy titanium (Ti (i-OC₄H₉)₄), four titanium n-butoxide (Ti (OC₄H₉)₄), triethoxy Methoxyl group titanium (Ti (OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy titanium (Ti (OCH₃)₂(OCH₃CH₂)₂), trimethoxy second Epoxide titanium (Ti (OCH₃)₃(OCH₃CH₂)), three isobutoxy methoxyl group titanium (Ti (OCH₃)(i-OC₄H₉)₃), two isobutoxy diformazans Epoxide titanium (Ti (OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutoxy titanium (Ti (OCH₃)₃(i-OC₄H₉)), three isobutoxy second Epoxide titanium (Ti (OCH₃CH₂)(i-OC₄H₉)₃), two isobutoxy diethoxy titanium (Ti (OCH₃CH₂)₂(i-OC₄H₉)₂), three ethoxies Base isobutoxy titanium (Ti (OCH₃CH₂)₃(i-OC₄H₉)), three n-butoxy methoxyl group titanium (Ti (OCH₃)(OC₄H₉)₃), two positive fourths Epoxide dimethoxy titanium (Ti (OCH₃)₂(OC₄H₉)₂), trimethoxy titanium n-butoxide (Ti (OCH₃)₃(OC₄H₉)), three positive fourth oxygen Ylmethoxy titanium (Ti (OCH₃CH₂)(OC₄H₉)₃), two n-butoxy diethoxy titanium (Ti (OCH₃CH₂)₂(OC₄H₉)₂), three ethoxies Base titanium n-butoxide (Ti (OCH₃CH₂)₃(OC₄H₉)) etc.；

Tetramethoxy zirconium (Zr (OCH₃)₄), tetraethoxy zirconium (Zr (OCH₃CH₂)₄), four isobutoxy zirconium (Zr (i-OC₄H₉ )₄), four n-butoxy zirconium (Zr (OC₄H₉)₄), triethoxy methoxyl group zirconium (Zr (OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy Base zirconium (Zr (OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethyoxyl zirconium (Zr (OCH₃)₃(OCH₃CH₂)), three isobutoxy methoxyl groups Zirconium (Zr (OCH₃)(i-OC₄H₉)₃), two isobutoxy dimethoxy zirconium (Zr (OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutyl oxygen Base zirconium (Zr (OCH₃)₃(i-C₄H₉)), three isobutoxy ethyoxyl zirconium (Zr (OCH₃CH₂)(i-OC₄H₉)₃), two isobutoxy diethyls Epoxide zirconium (Zr (OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy zirconium (Zr (OCH₃CH₂)₃(i-OC₄H₉)), three positive fourth oxygen Ylmethoxy zirconium (Zr (OCH₃)(OC₄H₉)₃), two n-butoxy dimethoxy zirconium (Zr (OCH₃)₂(OC₄H₉)₂), trimethoxy just Butoxy zirconium (Zr (OCH₃)₃(OC₄H₉)), three n-butoxy methoxyl group zirconium (Zr (OCH₃CH₂)(OC₄H₉)₃), two n-butoxies two Ethyoxyl zirconium (Zr (OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy zirconium (Zr (OCH₃CH₂)₃(OC₄H₉)) etc.；

Tetramethoxy hafnium (Hf (OCH₃)₄), tetraethoxy hafnium (Hf (OCH₃CH₂)₄), four isobutoxy hafnium (Hf (i-OC₄H₉ )₄), four n-butoxy hafnium (Hf (OC₄H₉)₄), triethoxy methoxyl group hafnium (Hf (OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy Base hafnium (Hf (OCH₃)₂(OCH₃CH₂)₂), trimethoxy ethyoxyl hafnium (Hf (OCH₃)₃(OCH₃CH₂)), three isobutoxy methoxyl groups Hafnium (Hf (OCH₃)(i-OC₄H₉)₃), two isobutoxy dimethoxy hafnium (Hf (OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutyl oxygen Base hafnium (Hf (OCH₃)₃(i-OC₄H₉)), three isobutoxy ethyoxyl hafnium (Hf (OCH₃CH₂)(i-OC₄H₉)₃), two isobutoxies two Ethyoxyl hafnium (Hf (OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy hafnium (Hf (OCH₃CH₂)₃(i-C₄H₉)), three positive fourths Oxymethoxy hafnium (Hf (OCH₃)(OC₄H₉)₃), two n-butoxy dimethoxy hafnium (Hf (OCH₃)₂(OC₄H₉)₂), trimethoxy N-butoxy hafnium (Hf (OCH₃)₃(OC₄H₉)), three n-butoxy methoxyl group hafnium (Hf (OCH₃CH₂)(OC₄H₉)₃), two n-butoxies Diethoxy hafnium (Hf (OCH₃CH₂)₂(OC₄H₉)₂), triethoxy n-butoxy hafnium (Hf (OCH₃CH₂)₃(OC₄H₉)) etc..

As described Group IVB metal alkyl halides, trimethyl ammonia chloride titanium (TiCl (CH such as can be enumerated₃)₃), three second Base titanium chloride (TiCl (CH₃CH₂)₃), triisobutyl titanium chloride (TiCl (i-C₄H₉)₃), three n-butylmagnesium chloride titanium (TiCl (C₄H₉)₃), dimethyl titanium chloride (TiCl₂(CH₃)₂), diethyl titanium chloride (TiCl₂(CH₃CH₂)₂), diisobutyl dichloro Change titanium (TiCl₂(i-C₄H₉)₂), three n-butylmagnesium chloride titanium (TiCl (C₄H₉)₃), methyl titanous chloride. (Ti (CH₃)Cl₃), ethyl three Titanium chloride (Ti (CH₃CH₂)Cl₃), isobutyl group titanous chloride. (Ti (i-C₄H₉)Cl₃), normal-butyl titanous chloride. (Ti (C₄H₉)Cl₃)；

Trimethyl titanium bromide (TiBr (CH₃)₃), triethyl group titanium bromide (TiBr (CH₃CH₂)₃), triisobutyl titanium bromide (TiBr (i-C₄H₉)₃), three normal-butyl titanium bromide (TiBr (C₄H₉)₃), dimethyl dibrominated titanium (TiBr₂(CH₃)₂), diethyl two Titanium bromide (TiBr₂(CH₃CH₂)₂), diisobutyl dibrominated titanium (TiBr₂(i-C₄H₉)₂), three normal-butyl titanium bromide (TiBr (C₄H₉)₃), methyl titanium tribromide (Ti (CH₃)Br₃), ethyl titanium tribromide (Ti (CH₃CH₂)Br₃), isobutyl group titanium tribromide (Ti (i-C₄H₉)Br₃), normal-butyl titanium tribromide (Ti (C₄H₉)Br₃)；

Trimethyl ammonia chloride zirconium (ZrCl (CH₃)₃), triethyl group zirconium chloride (ZrCl (CH₃CH₂)₃), triisobutyl zirconium chloride (ZrCl (i-C₄H₉)₃), three n-butylmagnesium chloride zirconium (ZrCl (C₄H₉)₃), dimethyl zirconium dichloride (ZrCl₂(CH₃)₂), diethyl two Zirconium chloride (ZrCl₂(CH₃CH₂)₂), diisobutyl zirconium dichloride (ZrCl₂(i-C₄H₉)₂), three n-butylmagnesium chloride zirconium (ZrCl (C₄H₉)₃), methyl tri-chlorination zirconium (Zr (CH₃)Cl₃), ethyl tri-chlorination zirconium (Zr (CH₃CH₂)Cl₃), isobutyl group tri-chlorination zirconium (Zr (i-C₄H₉)Cl₃), normal-butyl tri-chlorination zirconium (Zr (C₄H₉)Cl₃)；

Trimethyl zirconium bromide (ZrBr (CH₃)₃), triethyl group zirconium bromide (ZrBr (CH₃CH₂)₃), triisobutyl zirconium bromide (ZrBr (i-C₄H₉)₃), three normal-butyl zirconium bromide (ZrBr (C₄H₉)₃), dimethyl dibrominated zirconium (ZrBr₂(CH₃)₂), diethyl two Zirconium bromide (ZrBr₂(CH₃CH₂)₂), diisobutyl dibrominated zirconium (ZrBr₂(i-C₄H₉)₂), three normal-butyl zirconium bromide (ZrBr (C₄H₉)₃), methyl tribromide zirconium (Zr (CH₃)Br₃), ethyl tribromide zirconium (Zr (CH₃CH₂)Br₃), isobutyl group tribromide zirconium (Zr (i-C₄H₉)Br₃), normal-butyl tribromide zirconium (Zr (C₄H₉)Br₃)；

Trimethyl ammonia chloride hafnium (HfCl (CH₃)₃), triethyl group hafnium chloride (HfCl (CH₃CH₂)₃), triisobutyl hafnium chloride (HfCl (i-C₄H₉)₃), three n-butylmagnesium chloride hafnium (HfCl (C₄H₉)₃), dimethyl hafnium dichloride (HfCl₂(CH₃)₂), diethyl two Hafnium chloride (HfCl₂(CH₃CH₂)₂), diisobutyl hafnium dichloride (HfCl₂(i-C₄H₉)₂), three n-butylmagnesium chloride hafnium (HfCl (C₄H₉)₃), methyl tri-chlorination hafnium (Hf (CH₃)Cl₃), ethyl tri-chlorination hafnium (Hf (CH₃CH₂)Cl₃), isobutyl group tri-chlorination hafnium (Hf (i-C₄H₉)Cl₃), normal-butyl tri-chlorination hafnium (Hf (C₄H₉)Cl₃)；

Trimethyl bromination hafnium (HfBr (CH₃)₃), triethyl group bromination hafnium (HfBr (CH₃CH₂)₃), triisobutyl bromination hafnium (HfBr (i-C₄H₉)₃), three normal-butyl bromination hafnium (HfBr (C₄H₉)₃), dimethyl dibrominated hafnium (HfBr₂(CH₃)₂), diethyl two Bromination hafnium (HfBr₂(CH₃CH₂)₂), diisobutyl dibrominated hafnium (HfBr₂(i-C₄H₉)₂), three normal-butyl bromination hafnium (HfBr (C₄H₉)₃), methyl tribromide hafnium (Hf (CH₃)Br₃), ethyl tribromide hafnium (Hf (CH₃CH₂)Br₃), isobutyl group tribromide hafnium (Hf (i-C₄H₉)Br₃), normal-butyl tribromide hafnium (Hf (C₄H₉)Br₃).

As described Group IVB metal alkoxide halogenide, trimethoxy titanium chloride (TiCl (OCH such as can be enumerated₃)₃), Triethoxy titanium chloride (TiCl (OCH₃CH₂)₃), three isobutoxy titanium chloride (TiCl (i-OC₄H₉)₃), three n-butoxy chlorinations Titanium (TiCl (OC₄H₉)₃), dimethoxy titanium chloride (TiCl₂(OCH₃)₂), diethoxy titanium chloride (TiCl₂ (OCH₃CH₂)₂), two isobutoxy titanium chloride (TiCl₂(i-OC₄H₉)₂), three n-Butoxyl titanium-chlorides (TiCl (OC₄H₉)₃), Methoxytitanium trichloride (Ti (OCH₃)Cl₃), ethyoxyl titanous chloride. (Ti (OCH₃CH₂)Cl₃), isobutoxy titanous chloride. (Ti (i-C₄H₉)Cl₃), nbutoxytitanium trichloride (Ti (OC₄H₉)Cl₃)；

Trimethoxy titanium bromide (TiBr (OCH₃)₃), triethoxy titanium bromide (TiBr (OCH₃CH₂)₃), three isobutoxy bromines Change titanium (TiBr (i-OC₄H₉)₃), three n-butoxy titanium bromide (TiBr (OC₄H₉)₃), dimethoxy dibrominated titanium (TiBr₂ (OCH₃)₂), diethoxy dibrominated titanium (TiBr₂(OCH₃CH₂)₂), two isobutoxy dibrominated titanium (TiBr₂(i-OC₄H₉)₂), Three n-butoxy titanium bromide (TiBr (OC₄H₉)₃), methoxyl group titanium tribromide (Ti (OCH₃)Br₃), ethyoxyl titanium tribromide (Ti (OCH₃CH₂)Br₃), isobutoxy titanium tribromide (Ti (i-C₄H₉)Br₃), n-butoxy titanium tribromide (Ti (OC₄H₉)Br₃)；

Trimethoxy zirconium chloride (ZrCl (OCH₃)₃), triethoxy zirconium chloride (ZrCl (OCH₃CH₂)₃), three isobutoxy chlorine Change zirconium (ZrCl (i-OC₄H₉)₃), three n-butoxy zirconium chloride (ZrCl (OC₄H₉)₃), dimethoxy zirconium dichloride (ZrCl₂ (OCH₃)₂), diethoxy zirconium dichloride (ZrCl₂(OCH₃CH₂)₂), two isobutoxy zirconium dichloride (ZrCl₂(i-OC₄H₉)₂), Three n-butoxy zirconium chloride (ZrCl (OC₄H₉)₃), methoxyl group tri-chlorination zirconium (Zr (OCH₃)Cl₃), ethyoxyl tri-chlorination zirconium (Zr (OCH₃CH₂)Cl₃), isobutoxy tri-chlorination zirconium (Zr (i-C₄H₉)Cl₃), n-butoxy tri-chlorination zirconium (Zr (OC₄H₉)Cl₃)；

Trimethoxy zirconium bromide (ZrBr (OCH₃)₃), triethoxy zirconium bromide (ZrBr (OCH₃CH₂)₃), three isobutoxy bromines Change zirconium (ZrBr (i-OC₄H₉)₃), three n-butoxy zirconium bromide (ZrBr (OC₄H₉)₃), dimethoxy dibrominated zirconium (ZrBr₂ (OCH₃)₂), diethoxy dibrominated zirconium (ZrBr₂(OCH₃CH₂)₂), two isobutoxy dibrominated zirconium (ZrBr₂(i-OC₄H₉)₂), Three n-butoxy zirconium bromide (ZrBr (OC₄H₉)₃), methoxyl group tribromide zirconium (Zr (OCH₃)Br₃), ethyoxyl tribromide zirconium (Zr (OCH₃CH₂)Br₃), isobutoxy tribromide zirconium (Zr (i-C₄H₉)Br₃), n-butoxy tribromide zirconium (Zr (OC₄H₉)Br₃)；

Trimethoxy hafnium chloride (HfCl (OCH₃)₃), triethoxy hafnium chloride (HfCl (OCH₃CH₂)₃), three isobutoxy chlorine Change hafnium (HfCl (i-OC₄H₉)₃), three n-butoxy hafnium chloride (HfCl (OC₄H₉)₃), dimethoxy hafnium dichloride (HfCl₂ (OCH₃)₂), diethoxy hafnium dichloride (HfCl₂(OCH₃CH₂)₂), two isobutoxy hafnium dichloride (HfCl₂(i-OC₄H₉)₂), Three n-butoxy hafnium chloride (HfCl (OC₄H₉)₃), methoxyl group tri-chlorination hafnium (Hf (OCH₃)Cl₃), ethyoxyl tri-chlorination hafnium (Hf (OCH₃CH₂)Cl₃), isobutoxy tri-chlorination hafnium (Hf (i-C₄H₉)Cl₃), n-butoxy tri-chlorination hafnium (Hf (OC₄H₉)Cl₃)；

Trimethoxy bromination hafnium (HfBr (OCH₃)₃), triethoxy bromination hafnium (HfBr (OCH₃CH₂)₃), three isobutoxy bromines Change hafnium (HfBr (i-OC₄H₉)₃), three n-butoxy bromination hafnium (HfBr (OC₄H₉)₃), dimethoxy dibrominated hafnium (HfBr₂ (OCH₃)₂), diethoxy dibrominated hafnium (HfBr₂(OCH₃CH₂)₂), two isobutoxy dibrominated hafnium (HfBr₂(i-OC₄H₉)₂), Three n-butoxy bromination hafnium (HfBr (OC₄H₉)₃), methoxyl group tribromide hafnium (Hf (OCH₃)Br₃), ethyoxyl tribromide hafnium (Hf (OCH₃CH₂)Br₃), isobutoxy tribromide hafnium (Hf (i-C₄H₉)Br₃), n-butoxy tribromide hafnium (Hf (OC₄H₉)Br₃).

As described Group IVB metallic compound, the most described Group IVB metal halide, more preferably TiCl₄、TiBr₄、 ZrCl₄、ZrBr₄、HfCl₄And HfBr₄, most preferably TiCl₄And ZrCl₄。

These Group IVB metallic compounds can be used alone one, or is applied in combination multiple with arbitrary ratio.

When described chemical treatments is liquid at normal temperatures, this chemical treatments can be directly used to carry out described chemistry Process reaction.When described chemical treatments is solid-state at normal temperatures, in order to measure with easy to operate for the sake of, preferably with solution Form uses described chemical treatments.Certainly, when described chemical treatments is liquid at normal temperatures, also may be used sometimes according to needs To use described chemical treatments as a solution, it is not particularly limited.

When preparing the solution of described chemical treatments, to the solvent now used, there is no particular limitation, as long as its This chemical treatments can be dissolved and do not destroy the existing carrier structure of (such as dissolving) described magnesium compound carrier.

Specifically, C can be enumerated_5-12Alkane, C_5-12Cycloalkane, halo C_5-12Alkane and halo C_5-12Cycloalkane etc., than As pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, Pentamethylene., hexamethylene, cycloheptane, ring can be enumerated Octane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro hendecane, chloro ten Dioxane and chlorocyclohexane etc., wherein preferred pentane, hexane, decane and hexamethylene, most preferably hexane.

These solvents can be used alone one, or is applied in combination multiple with arbitrary ratio.

It addition, to described chemical treatments concentration in its solution, there is no particular limitation, can be the most suitable Select, react to carry out described chemical treatment as long as it is capable of the described chemical treatments with scheduled volume.Such as front institute State, if chemical treatments is liquid, can directly use chemical treatments to carry out described process but it also may to be adjusted Use after making the solution of chemical treatments.

It is said that in general, the molar concentration that described chemical treatments is in its solution is usually set to 0.01 ~ 1.0mol/L, but It is not limited to this.

According to the present invention, the ways of carrying out reacted as described chemical treatment, such as can enumerate and make described magnesium compound Carrier connects in the presence of solvent (also referred to as chemical treatment solvent) with described silicon compound and described chemical treatments The mode touched.

According to the present invention, to described chemical treatment solvent, there is no particular limitation, as long as it can dissolve described silication Compound and described chemical treatments, and do not destroy the existing carrier structure of (such as dissolving) described magnesium compound carrier.

Specifically, as described chemical treatment solvent, C can be enumerated_5-12Alkane, C_5-12Cycloalkane, halo C_5-12Alkane Hydrocarbon and halo C_5-12Cycloalkane etc., such as can enumerate pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, Pentamethylene., hexamethylene, cycloheptane, cyclooctane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro Decane, chloro hendecane, chlorinated dodecane and chlorocyclohexane etc., wherein preferred pentane, hexane, decane and hexamethylene, optimum Select hexane.

These solvents can be used alone one, or is applied in combination multiple with arbitrary ratio.

According to the present invention, as the consumption of described chemical treatment solvent so that described magnesium compound carrier is relative to institute The ratio stating chemical treatment solvent is 1g:1-100ml, preferably 1g:2-40ml, but is sometimes not limited to this.It addition, When using chemical treatments the most as a solution, can suitably reduce described chemical treatment according to practical situation with molten The consumption of agent, but be not particularly limited.

According to the present invention, as the consumption of described silicon compound so that the described magnesium compound carrier in terms of Mg element with The mol ratio of the described silicon compound in terms of Si element reaches 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.05- 0.25。

According to the present invention, as the consumption of described chemical treatments so that the described magnesium compound carrier in terms of Mg element 1:0.01-1 is reached with the mol ratio of the described chemical treatments with Group IVB elemental metal, preferably 1:0.01-0.50, more excellent Select 1:0.10-0.30.

It is known that when using Group IVB metallic compound chemical treatment carrier, can be the most immobilized a certain amount of Group IVB metallic compound.The present inventor is found by research, in the Group IVB metallic compound that this is immobilized, has quite A big part is rendered as inactive state, i.e. this part Group IVB metallic compound is for the final loaded catalyst manufactured Olefinic polymerization catalysis activity do not contribute.To this end, the present inventor is by further investigation revealed that, if used During Group IVB metallic compound chemical treatment carrier and with the aforementioned specific silicon compound of the present invention, this nothing can be significantly decreased The ratio of active part or significantly decrease the supported quantity of described Group IVB metallic compound on carrier, thus correspondingly improve The load capacity of Nonmetallocene coordination compound or the load percentage relative to Group IVB metallic compound.Result is, and not and with described The situation of silicon compound is compared, the present invention and during with described silicon compound, the support type that can significantly improve final acquisition is non- The olefinic polymerization catalysis activity of metallocene catalyst.It addition, present inventor have further discovered that, by and with described silication close Thing, it is also possible to realize narrowing molecular weight distribution, improves mechanical properties of polymer, and makes comonomer in the polymer The sequence the most regular function of distribution.These discoveries are the most all Promethean.

According to the present invention, to described magnesium compound carrier and described silicon compound and the engagement sequence of described chemical treatments There is no particular limitation, and such as this three can contact simultaneously, it is also possible to according to arbitrary order successively contact.

According to one preferred embodiment of the invention, in the presence of described chemical treatment solvent, make described magnesium Compound carrier first contacts (the first contact procedure) with described silicon compound, then adds described chemical treatments and carries out further Contact (the second contact procedure), thus carry out described chemical treatment reaction.

As the ways of carrying out of described first contact procedure, such as can enumerate under agitation, described magnesium compound is carried Body and described silicon compound simultaneously or successively add in described chemical treatment solvent, continue under 0-100 DEG C (preferably 20-80 DEG C) Continuous stirring also reacts and forms the mode of slurry.To the response time now, there is no particular limitation, such as can enumerate 0-6h, preferably 0.5-4h.

After obtaining slurry as previously mentioned, this slurry is made further to be contacted (with described chemical treatments Two contact procedures).

As the ways of carrying out of described second contact procedure, such as can enumerate under agitation, add in described slurry (preferably dropping) described chemical treatments or the solution of described chemical treatments, and after this addition terminates, at 0-100 DEG C Stirring the mode reacted is continued under (preferably 20-80 DEG C).To the response time now, there is no particular limitation, such as can lift Go out 0.5-8h, preferably 1-4h.

After described chemical treatment reaction terminates, by being filtered, washed and dried, can obtain through chemically treated product Thing (load type non-metallocene catalyst of the present invention).

According to the present invention, described in be filtered, washed and dried conventional method can be used to carry out, wherein washer solvent is permissible Use the solvent same with described chemical treatment solvent phase.As required, this washing typically carries out 1～8 time, preferably 2～6 times, Most preferably 2～4 times.

Described being dried can use conventional method to carry out, under such as noble gas seasoning, boulton process or vacuum Heat drying method, preferably noble gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum seasoning.Described dry Dry temperature range is generally room temperature to 140 DEG C, is generally drying time 2-20 hour, but is not limited to this.

According to the present invention, the preparation method of described load type non-metallocene catalyst as required, is optionally additionally included in and makes Before described magnesium compound carrier contacts with described silicon compound and described chemical treatments, with selected from aikyiaiurnirsoxan beta, alkyl aluminum or The step (pre-treatment step) helping magnesium compound carrier described in chemical treatments pretreatment of its combination in any.

In the context of the present specification, unless specifically stated otherwise or the most unreasonable, without exception will be through this pretreatment Magnesium compound carrier is also referred to as magnesium compound carrier.

Chemical treatments is helped to be specifically described to described below.

According to the present invention, help chemical treatments as described, such as can enumerate aikyiaiurnirsoxan beta and alkyl aluminum.

As described aikyiaiurnirsoxan beta, such as can enumerate the linear alumoxanes shown in following logical formula (I): (R) (R) Al-(Al (R)-O)_n-O-Al (R) (R), and the Cyclic aluminoxane shown in following logical formula (II) :-(Al (R)-O-)_n+2-。

(I)(II)

In aforementioned formula, group R is same to each other or different to each other (the most identical), is each independently selected from C₁-C₈Alkyl, excellent Select methyl, ethyl and isobutyl group, most preferable；N is the arbitrary integer in the range of 1-50, any in the range of preferably 10～30 Integer.

As described aikyiaiurnirsoxan beta, preferably MAO, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, Further preferably MAO and isobutyl aluminium alkoxide.

These aikyiaiurnirsoxan beta can be used alone one, or is applied in combination multiple with arbitrary ratio.

As described alkyl aluminum, the compound shown in below formula such as can be enumerated:

Al(R)₃

Wherein, group R is same to each other or different to each other (the most identical), and is each independently selected from C₁-C₈Alkyl, preferably first Base, ethyl and isobutyl group, most preferable.

Specifically, as described alkyl aluminum, trimethyl aluminium (Al (CH such as can be enumerated₃)₃), triethyl aluminum (Al (CH₃CH₂)₃), tri-n-n-propyl aluminum (Al (C₃H₇)₃), triisopropylaluminiuand (Al (i-C₃H₇)₃), triisobutyl aluminium (Al (i-C₄H₉)₃), Three n-butylaluminum (Al (C₄H₉)₃), triisopentyl aluminum (Al (i-C₅H₁₁)₃), three n-pentyl aluminum (Al (C₅H₁₁)₃), tri-n-hexyl aluminum (Al (C₆H₁₃)₃), three isohesyl aluminum (Al (i-C₆H₁₃)₃), diethylmethyl aluminum (Al (CH₃)(CH₃CH₂)₂) and dimethyl ethyl Aluminum (Al (CH₃CH₂)(CH₃)₂) etc., wherein preferred trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, most preferably three Aluminium ethide and triisobutyl aluminium.

These alkyl aluminums can be used alone one, or is applied in combination multiple with arbitrary ratio.

According to the present invention, help chemical treatments as described, it is possible to use only described aikyiaiurnirsoxan beta, it is also possible to only with described Alkyl aluminum but it also may use described aikyiaiurnirsoxan beta and any mixture of described alkyl aluminum.And, to component each in this mixture Ratio there is no particular limitation, can the most arbitrarily select.

According to the present invention, described in help chemical treatments to be usually to use as a solution.Chemistry is being helped described in preparation During the solution of inorganic agent, to the solvent now used, there is no particular limitation, as long as it can dissolve this helps chemical treatments And do not destroy the existing carrier structure of (such as dissolving) described magnesium compound carrier.

Specifically, C can be enumerated_5-12Alkane, C_5-12Cycloalkane, halo C_5-12Alkane and halo C_5-12Cycloalkane etc., than As pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, Pentamethylene., hexamethylene, cycloheptane, ring can be enumerated Octane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro hendecane, chloro ten Dioxane and chlorocyclohexane etc., wherein preferred pentane, hexane, decane and hexamethylene, most preferably hexane.

These solvents can be used alone one, or is applied in combination multiple with arbitrary ratio.

It addition, help chemical treatments concentration in its solution to described there is no particular limitation, can fit as required Work as selection, as long as it is capable of helping chemical treatments to carry out described pre-treatment step described in scheduled volume.

As the method carrying out described pre-treatment step, such as can enumerate, first prepare described in help chemical treatments Solution, then to intend with described in help metering in the described magnesium compound carrier of chemical treatments pretreatment to add (preferably dropping) Described help chemical treatment agent solution (wherein contain and help chemical treatments described in scheduled volume), or help chemical treatments to described In solution, metering adds described magnesium compound carrier, is consequently formed reaction mixture.Now, reaction temperature generally-40 ~ 60 DEG C, preferably-30 ~ 30 DEG C, the response time is generally 1 ~ 8h, preferably 2 ~ 6h, and most preferably 3 ~ 4h(is if desired by stirring).Then, By being filtered, washed and dried, from this reaction mixture, isolate the magnesium compound carrier through pretreatment.Then, use This is through the magnesium compound carrier of pretreatment, according to exact same way is described before, carry out and silicon compound and chemistry The contact of inorganic agent.

According to the present invention, described in be filtered, washed and dried conventional method can be used to carry out, wherein washer solvent is permissible Use and identical solvent used when helping chemical treatments described in dissolving.As required, this washing typically carries out 1～8 time, preferably 2～6 times, most preferably 2～4 times.Described being dried can use conventional method to carry out, such as noble gas seasoning, vacuum drying Method or heating under vacuum seasoning, preferably noble gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum Seasoning.Described dry temperature range is generally room temperature to 140 DEG C, is generally drying time 2-20 hour, but is not limited to This.

According to the present invention, as the consumption of described Nonmetallocene part so that the described magnesium compound in terms of Mg element with The mol ratio of described Nonmetallocene part is 1:0.0001-1, preferably 1:0.0002-0.4, more preferably 1:0.0008-0.2, enters one Walk preferred 1:0.001-0.1.

According to the present invention, as the consumption of described solvent so that described magnesium compound is 1mol with the ratio of described solvent: 75～400ml, preferably 1mol:150～300ml, more preferably 1mol:200～250ml.

According to the present invention, as the consumption of described alcohol so that the described magnesium compound in terms of Mg element rubs with described alcohol That ratio is 1:0.02～4.00, preferably 1:0.05～3.00, more preferably 1:0.10～2.50.

According to the present invention, as the consumption of described precipitant so that described precipitant is 1 with the volume ratio of described solvent: 0.2～5, preferably 1:0.5～2, more preferably 1:0.8～1.5.

According to the present invention, as the consumption of described silicon compound so that the described magnesium compound carrier in terms of Mg element with The mol ratio of the described silicon compound counted with Si element as 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.05-0.25.

According to the present invention, as the consumption of described chemical treatments so that the described magnesium compound carrier in terms of Mg element With the mol ratio of the described chemical treatments with Group IVB elemental metal as 1:0.01-1, preferably 1:0.01-0.50, more preferably 1:0.10-0.30.

According to the present invention, as the described consumption helping chemical treatments so that the described magnesium compound in terms of Mg element carries Body with count with Al element described in help the mol ratio of chemical treatments as 1:0-1.0, preferably 1:0-0.5, more preferably 1:0.1- 0.5。

Known to those skilled in the art, aforementioned all of method step is the most preferably at the bar of substantially anhydrous and oxygen-free Carry out under part.Mentioned here during substantially anhydrous and oxygen-free refers to system the content of water and oxygen continuously less than 100ppm.And, The load type non-metallocene catalyst of the present invention typically requires pressure-fired noble gas (such as nitrogen in confined conditions after the production Gas, argon, helium etc.) in the presence of save backup.

In one embodiment, the invention still further relates to by the preparation method system of aforesaid load type non-metallocene catalyst The load type non-metallocene catalyst (otherwise referred to as carry type non-metallocene calalyst for polymerization of olefine) made.

In a further embodiment, the present invention relates to a kind of alkene homopolymerization/copolymerization method, wherein with the present invention Load type non-metallocene catalyst as catalyst for olefines polymerizing, make alkene homopolymerization or copolymerization.

For this alkene homopolymerization/copolymerization method involved in the present invention, in addition to the following content particularly pointed out, its The content (such as polymerization reactor, alkene consumption, catalyst and the addition manner etc. of alkene) that he does not explains, can directly fit By conventionally known in the art those, being not particularly limited, at this, the description thereof will be omitted.

Homopolymerization/copolymerization method according to the present invention, with the load type non-metallocene catalyst of the present invention as major catalyst, with One or more in aikyiaiurnirsoxan beta, alkyl aluminum, haloalkyl aluminum, boron halothane, boron alkyl and boron alkyl ammonium salt are co-catalysis Agent, makes alkene homopolymerization or copolymerization.

Major catalyst and the promoter feed postition in polymerization reaction system can be first to add major catalyst, the most again Add promoter, or be initially charged promoter, then add major catalyst, or both first contact after mixing together Add, or be simultaneously introduced respectively.Both can depend in same Feed lines when major catalyst and promoter are separately added into Secondary addition, it is also possible to be sequentially added in multichannel Feed lines, and multichannel Feed lines should be selected when both are simultaneously introduced respectively. For continuous way polyreaction, preferably multichannel Feed lines is continuously added to simultaneously, and for intermittence type polymerization reacts, Preferably add together in same Feed lines after both first mixing, or be initially charged promoter in same Feed lines, Then major catalyst is added.

According to the present invention, to the reactive mode of described alkene homopolymerization/copolymerization method, there is no particular limitation, can use this Known to field, those, such as can enumerate slurry process, substance law and vapor phase method etc., wherein preferred slurries method and vapor phase method.

According to the present invention, as described alkene, C such as can be enumerated₂～C₁₀Monoolefine, diolefin, cyclic olefin and its His ethylenically unsaturated compounds.

Specifically, as described C₂～C₁₂Monoolefine, such as can enumerate ethylene, propylene, 1-butylene, 1-hexene, 1- Heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene and styrene etc.；As described ring-type alkene Hydrocarbon, such as can enumerate 1-cyclopentenes and norborene etc.；As described diolefin, such as can enumerate Isosorbide-5-Nitrae-butadiene, 2, 5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc.；And as other ethylenic unsaturation chemical combination described Thing, such as can enumerate vinylacetate and (methyl) acrylate etc..

According to the present invention, the homopolymerization of further preferred ethylene, or ethylene with selected from least one of C3-C12 alpha-olefin The copolymerization of alpha-olefin (referred to as comonomer).As described C3-C12 alpha-olefin more preferably C3-C8 alpha-olefin.As making herein Alpha-olefin, such as can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 4-methyl-1-pentene, 1- Laurylene and 4-methyl isophthalic acid-hexene etc., preferably propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene and 1-octene etc., more preferably Propylene, 1-hexene, 4-methyl-1-pentene and 1-octene etc..These alpha-olefins can be used alone, maybe can be by two in them Kind or more kinds of be applied in combination.

According to the present invention, in use, the usage amount of described comonomer is generally 0.5 ~ 10 gram/milligram major catalyst, Preferably 1 ~ 5 gram/milligram major catalyst.

According to the present invention, described promoter is selected from aikyiaiurnirsoxan beta, alkyl aluminum, haloalkyl aluminum, boron halothane, boron alkyl and alkane Base boron ammonium salt, wherein preferred at least one in aikyiaiurnirsoxan beta and alkyl aluminum.

As described aikyiaiurnirsoxan beta, such as can enumerate the linear alumoxanes shown in following formula (I-1): (R) (R) Al-(Al (R)-O)_n-O-Al (R) (R), and the Cyclic aluminoxane shown in following formula (II-1) :-(Al (R)-O-)_n+2-。

(I-1)(II-1)

In aforementioned formula, group R is same to each other or different to each other (the most identical), is each independently selected from C₁-C₈Alkyl, excellent Select methyl, ethyl and isobutyl group, most preferable.N is the arbitrary integer in the range of 1-50, any in the range of preferably 10～30 Integer.

As described aikyiaiurnirsoxan beta, preferably MAO, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, Further preferably MAO and isobutyl aluminium alkoxide, and most preferable aikyiaiurnirsoxan beta.

These aikyiaiurnirsoxan beta can be used alone one, or is applied in combination multiple with arbitrary ratio.

As described alkyl aluminum, the compound shown in below formula such as can be enumerated:

Al(R)₃

Wherein, group R is same to each other or different to each other (the most identical), and is each independently selected from C₁-C₈Alkyl, preferably first Base, ethyl and isobutyl group, most preferable.

Specifically, as described alkyl aluminum, trimethyl aluminium (Al (CH such as can be enumerated₃)₃), triethyl aluminum (Al (CH₃CH₂)₃), tri-n-n-propyl aluminum (Al (C₃H₇)₃), triisobutyl aluminium (Al (i-C₄H₉)₃), three n-butylaluminum (Al (C₄H₉)₃), three Isopentyl aluminum (Al (i-C₅H₁₁)₃), three n-pentyl aluminum (Al (C₅H₁₁)₃), tri-n-hexyl aluminum (Al (C₆H₁₃)₃), three isohesyl aluminum (Al (i-C₆H₁₃)₃), diethylmethyl aluminum (Al (CH₃)(CH₃CH₂)₂) and dimethyl ethyl aluminum (Al (CH₃CH₂)(CH₃)₂) etc., Wherein preferred trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum and triisobutyl aluminium, further preferred triethyl aluminum and triisobutyl Aluminum, and most preferably triethyl aluminum.

These alkyl aluminums can be used alone one, or is applied in combination multiple with arbitrary ratio.

As described haloalkyl aluminum, the compound shown in below formula such as can be enumerated:

Al(R)_nX_3-n

Wherein, group R is same to each other or different to each other (the most identical), and is each independently selected from C₁-C₈Alkyl, preferably first Base, ethyl and isobutyl group, most preferable.Group X is halogen, preferably chlorine.N is 1 or 2.

Specifically, as described haloalkyl aluminum, a Chlorodimethyl aluminum (Al (CH such as can be enumerated₃)₂Cl), dichloro Aluminium methyl (Al (CH₃)Cl₂)), aluminium diethyl monochloride (Al (CH₃CH₂)₂Cl), ethyl aluminum dichloride (Al (CH₃CH₂)Cl₂), a chlorine two Propyl group aluminum (Al (C₃H₇)₂Cl), two chloropropyl aluminum (Al (C₃H₇)Cl₂)), a chlorine di-n-butyl aluminum (Al (C₄H₉)₂Cl), dichloro is just Butyl aluminum (Al (C₄H₉)Cl₂), a chloro-di-isobutyl aluminum (Al (i-C₄H₉)₂Cl), dichloro aluminium isobutyl (Al (i-C₄H₉)Cl₂), one Chlorine two n-pentyl aluminum (Al (C₅H₁₁)₂Cl), dichloro n-pentyl aluminum (Al (C₅H₁₁)Cl₂), a chlorine diisoamyl aluminum (Al (i-C₅H₁₁)₂Cl), dichloro isopentyl aluminum (Al (i-C₅H₁₁)Cl₂), a chlorine di-n-hexyl aluminum (Al (C₆H₁₃)₂Cl), dichloro n-hexyl aluminum (Al (C₆H₁₃)Cl₂), a chlorine two isohesyl aluminum (Al (i-C₆H₁₃)₂Cl), dichloro isohesyl aluminum (Al (i-C₆H₁₃)Cl₂),

Chloromethyl aluminium ethide (Al (CH₃) (CH₃CH₂) Cl), chloromethyl propyl group aluminum (Al (CH₃) (C₃H₇) Cl), one Chloromethyl n-butylaluminum (Al (CH₃) (C₄H₉) Cl), chloromethyl aluminium isobutyl (Al (CH₃) (i-C₄H₉) Cl), a chloroethyl Propyl group aluminum (Al (CH₂CH₃) (C₃H₇) Cl), a chloroethyl n-butylaluminum (AlCH₂CH₃)(C₄H₉) Cl), chloromethyl aluminium isobutyl (AlCH₂CH₃)(i-C₄H₉) Cl) etc., wherein preferred aluminium diethyl monochloride, ethyl aluminum dichloride, a chlorine di-n-butyl aluminum, dichloro are just Butyl aluminum, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl, a chlorine di-n-hexyl aluminum, dichloro n-hexyl aluminum, further preferred chlorine two Aluminium ethide, ethyl aluminum dichloride and a chlorine di-n-hexyl aluminum, and most preferably aluminium diethyl monochloride.

These haloalkyl aluminum can be used alone one, or is applied in combination multiple with arbitrary ratio.

As described boron halothane, described boron alkyl and described boron alkyl ammonium salt, can directly use commonly used in the art Those, be not particularly limited.

It addition, according to the present invention, described promoter can be used alone one, it is also possible to as required with arbitrarily than Example is applied in combination multiple aforesaid promoter, is not particularly limited.

According to the present invention, according to the difference (such as slurry polymerization) of the reactive mode of described alkene homopolymerization/copolymerization method, have Time need use solvent for polymerization.

As described solvent for polymerization, it is possible to use this area when carrying out alkene homopolymerization/copolymerization conventional use of those, It is not particularly limited.

As described solvent for polymerization, C such as can be enumerated_4-10Alkane (such as butane, pentane, hexane, heptane, octane, Nonane or decane etc.), halo C_1-10Alkane (such as dichloromethane), C_6-12Cycloalkane (hexamethylene, cycloheptane, cyclooctane, ring nonyl Alkane or cyclodecane), C_6-20Aromatic hydrocarbon (such as toluene and dimethylbenzene) etc..Wherein, pentane, hexane, heptane and hexamethylene are preferably used Alkane is as described solvent for polymerization, most preferably hexane.

These solvent for polymerization can be used alone one, or is applied in combination multiple with arbitrary ratio.

According to the present invention, the polymerization pressure of described alkene homopolymerization/copolymerization method is generally 0.1～10MPa, preferably 0.1～4MPa, more preferably 0.4～3MPa, but sometimes it is not limited to this.According to the present invention, polymeric reaction temperature generally-40 DEG C～200 DEG C, preferably 10 DEG C～100 DEG C, more preferably 40 DEG C～95 DEG C, but be sometimes not limited to this.

It addition, according to the present invention, described alkene homopolymerization/copolymerization method can be carried out, also under conditions of with the presence of hydrogen Can carry out under conditions of there is no hydrogen.In case of presence, the dividing potential drop of hydrogen can be described polyreaction pressure The 0.01%～99% of power, preferably 0.01%～50%, but sometimes it is not limited to this.

According to the present invention, when carrying out described alkene homopolymerization/copolymerization method, the described promoter in terms of aluminum or boron with The mol ratio of the described load type non-metallocene catalyst of described central metal atom meter be generally 1～1000:1, preferably 10～ 500:1, more preferably 15～300:1, but sometimes it is not limited to this.

Embodiment

Hereinafter use embodiment that the present invention is described in further detail, but the present invention is not limited to these embodiments.

(unit is g/cm to polymer stacks density³) mensuration carry out with reference to CNS GB 1636-79.

In load type non-metallocene catalyst, the content of IV B race metal (such as Ti) and Mg element uses ICP-AES method to survey Fixed, the content of Nonmetallocene part or coordination compound uses elemental microanalysis method to measure.

The polymerization activity of catalyst calculates in accordance with the following methods: after polyreaction terminates, by the polymerization in reactor Product filters and is dried, and then weighs the quality of this polymerizate, with this polymerizate quality divided by the non-cyclopentadienyl of support type used The ratio of the quality of metallic catalyst represent this catalyst polymerization activity (unit be kg polymer/g catalyst or kg polymerization Thing/gCat).

Molecular weight Mw, Mn of polymer and molecular weight distribution (Mw/Mn) use the GPC V2000 type of WATERS company of the U.S. Gel chromatography analyser is measured, and with 1,2,4-trichloro-benzenes are solvent, and temperature during mensuration is 150 DEG C.

The viscosity-average molecular weight of polymer calculates in accordance with the following methods: according to standard ASTM D4020-00, uses high temperature dilution (capillary inner diameter is 0.44mm to type Ubbelohde viscometer method, and constant temperature bath medium is No. 300 silicone oil, and dilution solvent is decahydronaphthalene, surveys Fixed temperature is 135 DEG C) measure the intrinsic viscosity of described polymer, divide equally then according to equation below calculates the viscous of described polymer Son amount Mv.

Wherein, η is intrinsic viscosity.

Embodiment 1

Magnesium compound uses anhydrous magnesium chloride, and solvent uses oxolane, and alcohol uses n-butyl alcohol, and silicon compound uses tetrem Epoxide silicon, the chemical treatments of Group IVB metallic compound uses titanium tetrachloride, and precipitant uses hexane, and Nonmetallocene part is adopted By structure it isCompound.

Weigh 5g anhydrous magnesium chloride, be completely dissolved under room temperature after adding solvent, Nonmetallocene part and alcohol, obtain magnesium chemical combination Thing solution, adds precipitant to magnesium compound solution and is allowed to precipitate completely, filter, and uses precipitant to wash 3 times, each precipitant Consumption is 60ml, is uniformly heated to evacuation at 60 DEG C and is dried to obtain magnesium compound carrier.

Joining in hexane solvent by prepared magnesium compound carrier, room temperature drips silicon compound and 30 points in lower 10 minutes Being added dropwise to Group IVB chemical treatments in clock, after being then uniformly heated to 60 DEG C of isothermal reactions 2 hours, filter, hexane solvent washs 3 times, each consumption is identical with the quantity of solvent added before, and finally at 60 DEG C, evacuation is dried, and obtains load type non-metallocene Catalyst.

Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:210ml；Magnesium compound and alcohol mol ratio are 1:0.5； Magnesium compound is 1:0.08 with the mol ratio of Nonmetallocene part；Precipitant and solvent volume proportioning are 1:1；In terms of Mg element The mol ratio of magnesium compound carrier and the silicon compound counted with Si element is as 1:0.1；Magnesium compound carrier in terms of Mg element with With the chemical treatments mol ratio of Group IVB elemental metal as 1:0.15.

Load type non-metallocene catalyst is designated as CAT-1.

Embodiment 2

Substantially the same manner as Example 1, but be with the following changes:

Before magnesium compound carrier contacts with described silicon compound and described chemical treatments, first pass through and help chemical treatments Triethyl aluminum processes magnesium compound carrier.

That is, magnesium compound carrier is joined in hexane solvent, then be slowly added dropwise and help chemical treatments triethyl aluminum (concentration For 0.88mol/L, hexane solution), stir at 60 DEG C after 2 hours and filter, hexane washs 3 times, each consumption with add before Quantity of solvent is identical, and finally at 60 DEG C, evacuation is dried, and obtains the magnesium compound carrier of pretreatment.The wherein magnesium in terms of Mg element Compound carrier with count with Al element help the mol ratio of chemical treatments as 1:0.2.

Load type non-metallocene catalyst is designated as CAT-2.

Embodiment 3

Substantially the same manner as Example 1, but be with the following changes:

Before magnesium compound carrier contacts with described silicon compound and described chemical treatments, first pass through and help chemical treatments MAO processes magnesium compound carrier.

That is, magnesium compound carrier is joined in toluene solvant, then be slowly added dropwise and help chemical treatments MAO (dense Degree is 10wt%, toluene solution), filter after stirring 2 hours at 60 DEG C, toluene washs 3 times, and each consumption is molten with add before Dosage is identical, and finally at 100 DEG C, evacuation is dried, and obtains the magnesium compound carrier of pretreatment.The wherein magnesium in terms of Mg element Compound carrier with count with Al element help the mol ratio of chemical treatments as 1:0.4.

Load type non-metallocene catalyst is designated as CAT-3.

Embodiment 4

Substantially the same manner as Example 1, but be with the following changes:

Magnesium compound changes into magnesium ethide (Mg (C₂H₅)₂), alcohol uses ethanol, and toluene changed into by solvent, and silicon compound changes into Tetraisobutoxy-silicane, the chemical treatments of Group IVB metallic compound changes into Zirconium tetrachloride. (ZrCl₄), precipitant changes hexamethylene into Alkane, Nonmetallocene part uses。

Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:150ml；Magnesium compound and alcohol mol ratio are 1:1.64； Magnesium compound is 1:0.04 with the mol ratio of Nonmetallocene part；Precipitant and solvent volume proportioning are 1:2；In terms of Mg element The mol ratio of magnesium compound carrier and the silicon compound counted with Si element as 1:0.05, the magnesium compound carrier in terms of Mg element with With the chemical treatments mol ratio of Group IVB elemental metal as 1:0.20.

Load type non-metallocene catalyst is designated as CAT-4.

Embodiment 5

Substantially the same manner as Example 1, but be with the following changes:

Magnesium compound changes into anhydrous magnesium bromide (MgBr₂), trichlorine methanol changed into by alcohol, and Nonmetallocene part uses, solvent changes into ethylbenzene, and silicon compound changes triethoxy chloro silicon into, Group IVB metallic compound Chemical treatments changes into titanium tetrabromide (TiBr₄).

Add in magnesium compound solution precipitant filtration washing drying steps change into directly at 110 DEG C evacuation do Dry obtain magnesium compound carrier.

Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:250ml；Magnesium compound and alcohol mol ratio are 1:1；Magnesium Compound is 1:0.2 with the mol ratio of Nonmetallocene part；Magnesium compound carrier in terms of Mg element and the silicon in terms of Si element The mol ratio of compound is 1:0.25, the magnesium compound carrier in terms of Mg element and the chemical treatment with Group IVB elemental metal Agent mol ratio is 1:0.30.

Load type non-metallocene catalyst is designated as CAT-5.

Embodiment 6

Substantially the same manner as Example 1, but be with the following changes:

Magnesium compound changes into ethyoxyl magnesium chloride (MgCl (OC₂H₅)), 2-Ethylhexyl Alcohol changed into by alcohol, and Nonmetallocene is joined Body uses, solvent changes into dimethylbenzene, and silicide changes Silicon chloride. into, Group IVB metallic compound Chemical treatments changes into tetraethyl titanium (Ti (CH₃CH₂)₄), decane changed into by precipitant.

Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:300ml；Magnesium compound and alcohol mol ratio are 1:0.25； Magnesium compound is 1:0.05 with the mol ratio of Nonmetallocene part；Precipitant and solvent volume proportioning are 1:1.5；In terms of Mg element Magnesium compound carrier as 1:0.14, in terms of Mg element of the mol ratio of magnesium compound carrier and the silicon compound counted with Si element With with the chemical treatments mol ratio of Group IVB elemental metal as 1:0.05.

Load type non-metallocene catalyst is designated as CAT-6.

Embodiment 7

Substantially the same manner as Example 1, but be with the following changes:

Magnesium compound changes into magnesium ethylate (Mg (OC₂H₅)₂), phenethanol changed into by alcohol, and Nonmetallocene part uses, solvent changes into diethylbenzene, and silicon compound changes tetramethoxy-silicane, Group IVB metal compound into The chemical treatments of thing changes into tetra-n-butyl titanium (Ti (C₄H₉)₄), pentane changed into by precipitant.

Wherein proportioning is, magnesium compound and solvent burden ratio are 1mol:400ml；Magnesium compound and alcohol mol ratio are 1:2.5； Magnesium compound is 1:0.4 with the mol ratio of Nonmetallocene part；Precipitant and solvent volume proportioning are 1:0.5；In terms of Mg element Magnesium compound carrier as 1:0.45, in terms of Mg element of the mol ratio of magnesium compound carrier and the silicon compound counted with Si element With with the chemical treatments mol ratio of Group IVB elemental metal as 1:0.50.

Load type non-metallocene catalyst is designated as CAT-7.

Embodiment 8

Substantially the same manner as Example 1, but be with the following changes:

Magnesium compound changes into methyl-magnesium-chloride (Mg (CH₃) Cl), alcohol changes Hexalin into, and Nonmetallocene part uses, it is the mixture of 1:1 that silicon compound changes into by tetraethoxy-silicane and Silicon chloride. according to mol ratio, Chlorotoluene changed into by solvent.

Wherein proportioning is, magnesium compound and alcohol mol ratio are 1:3.0；Magnesium compound with the mol ratio of Nonmetallocene part is 1:0.01；The mol ratio of the magnesium compound carrier counted with Mg element and the silicon compound counted with Si element is as 1:0.02, with Mg unit The magnesium compound carrier of element meter with the chemical treatments mol ratio of Group IVB elemental metal as 1:0.10.

Load type non-metallocene catalyst is designated as CAT-8.

Comparative example A

Substantially the same manner as Example 1, but be with the following changes:

In load type non-metallocene catalyst preparation process, magnesium compound carrier processes without silicon compound, but directly It is added dropwise to Group IVB chemical treatments process；

Catalyst is designated as CAT-A.

Comparative example B

Substantially the same manner as Example 1, but be with the following changes:

The mol ratio of the magnesium compound carrier counted with Mg element and the silicon compound counted with Si element is as 1:0.05.

Catalyst is designated as CAT-B.

Comparative example C

Substantially the same manner as Example 1, but be with the following changes:

The mol ratio of the magnesium compound carrier counted with Mg element and the silicon compound counted with Si element is as 1:0.20.

Catalyst is designated as CAT-C.

Comparative example D

Substantially the same manner as Example 1, but be with the following changes:

Magnesium compound solution preparation process is added without Nonmetallocene part；

Catalyst is designated as CAT-D.

Application Example

By the load type non-metallocene catalyst CAT-1～8, CAT-A～D that prepare in the embodiment of the present invention respectively following Under the conditions of carry out homopolymerization and the copolymerization of ethylene in accordance with the following methods:

Homopolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, is polymerized stagnation pressure 0.8MPa, polymerization temperature Spend 85 DEG C, hydrogen partial pressure 0.2MPa, 2 hours response time.First joining in polymerization autoclave by 2.5 liters of hexanes, unlatching is stirred Mix, be subsequently adding 20mg load type non-metallocene catalyst and catalyst mixture, add hydrogen to 0.2MPa, finally hold Continuous it be passed through ethylene and make polymerization stagnation pressure constant at 0.8MPa.After reaction terminates, gas reactor is vented, releases still interpolymer, dry Quality is weighed after dry.Concrete condition and the polymerization evaluation result of this polyreaction are as shown in table 1.

Copolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, is polymerized stagnation pressure 0.8MPa, polymerization temperature Spend 85 DEG C, hydrogen partial pressure 0.2MPa, 2 hours response time.First joining in polymerization autoclave by 2.5 liters of hexanes, unlatching is stirred Mix, be subsequently adding 20mg load type non-metallocene catalyst and catalyst mixture, disposably add hexene-1 comonomer 50g, adds hydrogen to 0.2MPa, is finally continually fed into ethylene and makes polymerization stagnation pressure constant at 0.8MPa.After reaction terminates, by still Interior gas is vented, and releases still interpolymer, weighs quality after drying.The concrete condition of this polyreaction and polymerization evaluation result As shown in table 1.

The homopolymerization of ultra-high molecular weight polyethylene is prepared in no hydrogen participation: 5 liters of polymerization autoclaves, slurry polymerization processes, and 2.5 Rise hexane solvent, be polymerized stagnation pressure 0.5MPa, polymerization temperature 70 DEG C, 2 hours response time.First 2.5 liters of hexanes are joined poly- Close in autoclave, open stirring, be subsequently adding 20mg load type non-metallocene catalyst and catalyst mixture, be warmed up to 60 Being continually fed into ethylene after DEG C makes polymerization stagnation pressure constant at 0.5MPa.After reaction terminates, gas reactor is vented, releases polymerization in still Thing, weighs quality after drying.Concrete condition and the polymerization evaluation result of this polyreaction are as shown in table 2.

Table 1. load type non-metallocene catalyst is used for olefinic polyreaction effect catalog

。

Table 2. load type non-metallocene catalyst is used for preparing ultra-high molecular weight polyethylene polyreaction effect catalog

。

From table 1, load type non-metallocene catalyst prepared by the method provided by the present invention is polymerized the polymerization obtained Thing molecular weight distribution is narrower, as it is known by the man skilled in the art that the general poly-second using Ziegler-Natta catalyst polymerization to obtain Alkene molecular weight distribution is more than 5.

Understood by the result of the test data of sequence number 3 and 4 in sequence number in table 12 and 3,5 and 7,8 and 10, and table 2, increase The consumption of promoter, i.e. improve promoter and catalyst activity metal molar than time, to polymerization catalyst activity and polymerization The impact of thing bulk density is the most notable.It can be said that bright, load type non-metallocene prepared by the method using the present invention to provide is urged Agent only needs fewer promoter consumption to be obtained with high olefin polymerizating activity；And the poly-second obtained by thus The polymer such as alkene have excellent polymer morphology and high polymer bulk density.

In contrast table 1, the result of the test data of sequence number 1 and 2,5 and 6,8 and 9 understand, and after copolymerization, catalyst activity has bigger The increase of amplitude, thus illustrate that load type non-metallocene catalyst prepared by the method using the present invention to provide has the most notable Comonomer effect.

By sequence number 1 and contrast sequence number 6 result of the test number in sequence number 1 in contrast table 1 and comparative example sequence number 16, and table 2 According to understanding, catalyst preparation process is added without silicon compound, although in catalyst, active metallic content is increased, but urges Agent polymerization activity and thus obtained polymer stacks density all reduce, and molecular weight distribution broadens, and the superelevation of preparation is divided Sub-weight northylen viscosity-average molecular weight is greatly lowered.

By sequence number 1 and comparative example sequence number 17 and 18 in contrast table 1, and sequence number 1 and the examination of contrast sequence number 7 and 8 in table 2 Test result data to understand, along with the increase of silicon compound addition in catalyst preparation process, active metallic content in catalyst Having obtained effective reduction, polymerization activity and the thus obtained polymer stacks density of catalyst all increased simultaneously, polymer Molecular weight distribution sharp, prepared ultra-high molecular weight polyethylene viscosity-average molecular weight increases, and thus explanation present invention introduces silication Compound has active metallic content invalid in effective reduction catalyst, improves catalyst activity and polymer stacks density simultaneously, Narrow molecular weight distribution, and improves the effect of ultra-high molecular weight polyethylene viscosity-average molecular weight.

By sequence number 1 and the result of the test of contrast sequence number 9 in sequence number 1 in contrast table 1 and comparative example sequence number 19, and table 2 Data understand, and do not introduce Nonmetallocene part in catalyst preparation process, and thus obtained catalyst belongs to Ziegler-Natta type Dynamics model catalyst, polymerization activity and polymer stacks density are relatively low, and molecular weight distribution is wider, prepared superelevation Molecular weight polyethylene viscosity-average molecular weight is relatively low.

Although the detailed description of the invention of the present invention has been described in detail the most in conjunction with the embodiments, however it is necessary that finger Going out, protection scope of the present invention is the most limited to these specific embodiments, but is come by claims of annex Determine.These embodiments can carried out by those skilled in the art without departing from the range of the technological thought of the present invention and purport Suitable change, and within the embodiment after these changes is obviously also included within protection scope of the present invention.

Claims (21)

1. a preparation method for load type non-metallocene catalyst, comprises the following steps:

Magnesium compound and Nonmetallocene part is made to be dissolved in the presence of an alcohol in solvent, it is thus achieved that the step of magnesium compound solution；

In described magnesium compound solution, add precipitant or be dried described magnesium compound solution, it is thus achieved that magnesium compound carrier Step；

Make the silicon compound of described magnesium compound carrier and lower formula (X) and connect selected from the chemical treatments of IV B race metallic compound Touch, it is thus achieved that the step of described load type non-metallocene catalyst,

Si(OR)_mX_4-mFormula (X)

Wherein, each R is identical or different, is each independently selected from C_1-8Straight or branched alkyl；M is the integer of 0,1,2,3 or 4； Each X is identical or different, is each independently selected from halogen,

Described preparation method is optionally additionally included in and makes described magnesium compound carrier and described silicon compound and described chemical treatments Before contact, with helping magnesium compound carrier described in chemical treatments pretreatment selected from aikyiaiurnirsoxan beta, alkyl aluminum or its combination in any Step.

2. according to the preparation method described in claim 1, it is characterised in that each R described is identical or different, selects independently of one another From C_1-4Straight or branched alkyl.

3. according to the preparation method described in claim 1, it is characterised in that each R described is ethyl.

4. according to the preparation method described in claim 1, it is characterised in that described magnesium compound is selected from magnesium halide, alkoxyl halogen Change one or more in magnesium, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium.

5. according to the preparation method described in claim 4, it is characterised in that described magnesium compound one in the magnesium halide or Multiple.

6. according to the preparation method described in claim 4, it is characterised in that described magnesium compound is magnesium chloride.

7. according to the preparation method described in claim 1, it is characterised in that described solvent is selected from C_6-12Aromatic hydrocarbon, halo C_6-12Virtue One or more in fragrant hydrocarbon, ester and ether, one or more in fatty alcohol, aromatic alcohol and alicyclic ring alcohol of described alcohol, wherein Described alcohol is optionally selected from halogen atom or C_1-6The substituent group of alkoxyl replaces.

8. according to the preparation method described in claim 7, it is characterised in that described solvent is selected from C_6-12Aromatic hydrocarbon and oxolane In one or more, one or more in ethanol and butanol of described alcohol.

9. according to the preparation method described in claim 1, it is characterised in that described Nonmetallocene part is selected from having following chemistry One or more in the compound of structural formula:

,

In above chemical structural formula,

Q is 0 or 1；

D is 0 or 1；

A selected from oxygen atom, sulphur atom, selenium atom,、-NR²³R²⁴、-N(O)R²⁵R²⁶、、-PR²⁸R²⁹、-P(O) R³⁰OR³¹, sulfuryl, sulfoxide group or-Se (O) R³⁹, wherein N, O, S, Se and P respectively coordination atom；

B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C₁-C₃₀Alkyl；

D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C₁-C₃₀Alkyl, sulfuryl Or sulfoxide group, wherein N, O, S, Se and P respectively coordination atom；

E selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are each From for coordination atom；

G is selected from C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or safing function group；

Represent singly-bound or double bond；

Represent covalent bond or ionic bond；

R¹To R³It is each independently selected from hydrogen, C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or safing function group, R²²To R³³ And R³⁹It is each independently selected from hydrogen, C₁-C₃₀Alkyl or substituted C₁-C₃₀Alkyl, above-mentioned group can identical also may be used to each other With difference, wherein adjacent group can combine togather bonding or cyclization,

Described substituted C₁-C₃₀Alkyl is selected from one or more halogens or C₁-C₃₀The C of alkyl alternatively base₁-C₃₀ Alkyl；

Described safing function group selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, Containing tin group, C₁-C₁₀Ester group and nitro,

Described halogen is selected from F, Cl, Br or I；

Described nitrogen-containing group is selected from、-NR²³R²⁴、-T-NR²³R²⁴Or-N (O) R²⁵R²⁶；

Described phosphorus-containing groups is selected from、-PR²⁸R²⁹、-P(O)R³⁰R³¹Or-P (O) R³²(OR³³)；

Described oxy radical is selected from-OR³⁴With-T-OR³⁴；

Described sulfur-containing group is selected from-SR³⁵、-T-SR³⁵、-S(O)R³⁶Or-T-SO₂R³⁷；

The described group containing seleno is selected from-SeR³⁸、-T-SeR³⁸、-Se(O)R³⁹Or-T-Se (O) R³⁹；

Described group T is selected from C₁-C₃₀Alkyl or substituted C₁-C₃₀Alkyl；

Described R³⁷Selected from hydrogen, C₁-C₃₀Alkyl or substituted C₁-C₃₀Alkyl；

Described C₁-C₃₀Alkyl is selected from C₁-C₃₀Alkyl, C₇-C₃₀Alkaryl, C₇-C₃₀Aralkyl, C₃-C₃₀Cyclic alkyl, C₂- C₃₀Thiazolinyl, C₂-C₃₀Alkynyl, C₆-C₃₀Aryl, C₈-C₃₀Condensed ring radical or C₄-C₃₀Heterocyclic radical, wherein said heterocyclic radical contains 1- 3 selected from nitrogen-atoms, oxygen atom or the hetero atom of sulphur atom；

Wherein, described silicon-containing group is selected from-SiR⁴²R⁴³R⁴⁴Or-T-SiR⁴⁵；Described germanic group is selected from-GeR⁴⁶R⁴⁷R⁴⁸Or-T- GeR⁴⁹；Described containing tin group selected from-SnR⁵⁰R⁵¹R⁵²、-T-SnR⁵³Or-T-Sn (O) R⁵⁴；

Described R³⁴To R³⁶、R³⁸And R⁴²To R⁵⁴It is each independently selected from hydrogen, C₁-C₃₀Alkyl or substituted C₁-C₃₀Alkyl, above-mentioned Group can be the same or different to each other, and wherein adjacent group can combine togather bonding or cyclization, and

Described group T is as previously defined.

10. according to the preparation method described in claim 9, it is characterised in that described Nonmetallocene part is selected from having followingization One or more in the compound (A) of structural formula and compound (B):

With,

(A) (B)

In above all of chemical structural formula,

F is selected from nitrogen-containing group or phosphorus-containing groups, wherein N and P respectively coordination atom.

11. according to the preparation method described in claim 10, it is characterised in that described Nonmetallocene part is selected from having followingization Learn the compound (A-1) of structural formula to compound (A-4) and compound (B-1) to compound (B-4) in one or more:

、、

(A-1) (A-2)

、、

(A-3) (A-4)

、、

(B-1) (B-2)

With,

(B-3) (B-4)

In above all of chemical structural formula,

Y is selected from-NR²³R²⁴、-N(O)R²⁵R²⁶、-PR²⁸R²⁹、-OR³⁴、-SR³⁵、-S(O)R³⁶、-SeR³⁸Or-Se (O) R³⁹, wherein N, O, S, Se and P respectively coordination atom；

Z selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are each From for coordination atom；

R⁴、R⁶To R²¹It is each independently selected from hydrogen, C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or safing function group, above-mentioned Group can be the same or different to each other, and wherein adjacent group can combine togather bonding or cyclization；And

R⁵Lone pair electrons, hydrogen, C on nitrogen₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl, oxy radical, sulfur-containing group, containing nitrilo Roll into a ball, containing seleno group or phosphorus-containing groups；Work as R⁵For oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or during phosphorus-containing groups, R⁵ In N, O, S, P and Se can be coordinated as coordination atom and center IV B race metallic atom.

12. according to the preparation method described in claim 11, it is characterised in that described Nonmetallocene part is selected from having followingization One or more in the compound of structural formula:

、、、、With。

13. according to the preparation method described in claim 12, it is characterised in that described Nonmetallocene part is selected from having followingization One or more in the compound of structural formula:

With。

14. according to the preparation method described in claim 1, it is characterised in that the described magnesium compound in terms of Mg element is with described The mol ratio of Nonmetallocene part is 1:0.0001-1, the ratio of described magnesium compound and described solvent be 1mol:75～ 400ml, the mol ratio of the described magnesium compound counted with Mg element and described alcohol is as 1:0.02～4.00, and described precipitant is with described The volume ratio of solvent is 1:0.2～5, the described magnesium compound carrier in terms of Mg element and the described silicon compound in terms of Si element Mol ratio be 1:0.01-1, the described magnesium compound carrier in terms of Mg element with the described chemistry of Group IVB elemental metal The mol ratio of inorganic agent is 1:0.01-1, and the described magnesium compound carrier in terms of Mg element helps described in terms of Al element The mol ratio of chemical treatments is 1:0-1.0.

15. according to the preparation method described in claim 14, it is characterised in that the described magnesium compound in terms of Mg element is with described The mol ratio of Nonmetallocene part is 1:0.001-0.1, the ratio of described magnesium compound and described solvent be 1mol:200～ 250ml, the mol ratio of the described magnesium compound counted with Mg element and described alcohol is as 1:0.10～2.50, and described precipitant is with described The volume ratio of solvent is 1:0.8～1.5, and the described magnesium compound carrier in terms of Mg element closes with the described silication in terms of Si element The mol ratio of thing is 1:0.05-0.25, the described magnesium compound carrier in terms of Mg element with described in Group IVB elemental metal The mol ratio of chemical treatments is 1:0.10-0.30, and the described magnesium compound carrier in terms of Mg element with in terms of Al element Described in help the mol ratio of chemical treatments be 1:0.1-0.5.

16. according to the preparation method described in claim 1, it is characterised in that described precipitant is selected from alkane, cycloalkane, halo One or more in alkane and halo cycloalkane.

17. according to the preparation method described in claim 16, it is characterised in that described precipitant selected from pentane, hexane, heptane, Octane, nonane, decane, hexamethylene, Pentamethylene., cycloheptane, cyclodecane, cyclononane, dichloromethane, dichloro hexane, two chloroheptanes, Chloroform, trichloroethane, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane, tribromo Butane, chlorocyclopentane, chlorocyclohexane, chloro cycloheptane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromo ring One or more in pentane, bromocyclohexane, bromo cycloheptane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane.

18. according to the preparation method described in claim 1, it is characterised in that described IV B race metallic compound is selected from IV B race gold Belonging to one or more in halogenide, described aikyiaiurnirsoxan beta is selected from MAO, ethylaluminoxane, isobutyl aluminium alkoxide and positive fourth One or more in base aikyiaiurnirsoxan beta, and described alkyl aluminum selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, Three n-butylaluminum, triisopentyl aluminum, three n-pentyl aluminum, three hexyl aluminum, three isohesyl aluminum, diethylmethyl aluminum and dimethyl ethyl One or more in aluminum.

19. according to the preparation method described in claim 18, it is characterised in that described IV B race metallic compound is selected from TiCl₄、 TiBr₄、ZrCl₄、ZrBr₄、HfCl₄And HfBr₄In one or more, described aikyiaiurnirsoxan beta be selected from MAO and aluminium isobutyl One or more in oxygen alkane, and described alkyl aluminum is in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium One or more.

20. 1 kinds of load type non-metallocene catalysts, it is by according to the preparation method system described in any one of claim 1-19 Make.

21. 1 kinds of alkene homopolymerization/copolymerization methods, it is characterised in that with according to the load type non-metallocene described in claim 20 Catalyst is major catalyst, with in aikyiaiurnirsoxan beta, alkyl aluminum, haloalkyl aluminum, boron halothane, boron alkyl and boron alkyl ammonium salt One or more are promoter, make alkene homopolymerization or copolymerization.