CN109485763A

CN109485763A - Load type non-metallocene catalyst, preparation method and its application

Info

Publication number: CN109485763A
Application number: CN201710814678.7A
Authority: CN
Inventors: 李传峰; 任鸿平; 汪文睿; 郭峰
Original assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Priority date: 2017-09-11
Filing date: 2017-09-11
Publication date: 2019-03-19

Abstract

The present invention relates to a kind of load type non-metallocene catalyst, preparation method and its applications.The preparation method of the load type non-metallocene catalyst is the following steps are included: the step of being dissolved in magnesium compound and Nonmetallocene ligand in solvent in the presence of an alcohol, obtain magnesium compound solution；The magnesium compound solution is dry, or the step of precipitating reagent is added into the magnesium compound solution, obtains modification carrier, wherein the content of alcohol described in the modification carrier is 3.0-5.0wt%；The step of handling the modification carrier with the chemical treatments selected from Group IVB metallic compound, obtain the load type non-metallocene catalyst.The load type non-metallocene catalyst such as has the characteristics that preparation method is simple and polymerization activity is flexibly adjustable.

Description

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

Technical field

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

Background technique

The non-metallocene catalyst that middle and later periods the 1990s occurs, also known as post-metallocene catalysts, in major catalyst Heart atom includes almost all of transition metal element, be after Ziegler, Ziegler-Natta and metallocene catalyst it Forth generation olefin polymerization catalysis afterwards, such catalyst has reached in certain performances or even more than metallocene catalysis Agent.Non-metallocene catalyst does not contain cyclopentadienyl group, and coordination atom is oxygen, nitrogen, sulphur and phosphorus, it is characterized in that central ion has There is stronger electrophilicity, and there is cis- alkyl or halogen metal division center, is easy to carry out alkene insertion and σ-key transfer, in Heart metal is easy alkylation, is conducive to the generation at cation activity center；The complex of formation has the geometric configuration limited, stands Body selectivity, electronegativity and chiral controllability.In addition, the metal-carbon key formed is easy polarization, conducive to the polymerization of alkene.Cause This, can obtain the olefin polymer of higher molecular weight under higher polymeric reaction temperature.

But it is short, easy that homogenous olefin polymerization catalyst has been found its active duration in olefin polymerization Viscous kettle, high methylaluminoxane dosage, and obtain that polymer molecular weight is too low or too high shortcoming, seriously limit it Industrial application.

One kind prepared by patent ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207 Alkene homopolymerization/copolymerization catalyst or catalyst system have extensive alkene homopolymerization/copolymerization performance, suitable for the poly- of diversified forms Technique is closed, but the catalyst disclosed in the patent or catalyst system need higher co-catalyst dosage in olefinic polymerization, Suitable olefin polymerizating activity could be obtained, and there is viscous kettle phenomenons in polymerization process.

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

For disclosed in patent ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207 Non-metallocene catalyst, patent CN1539855A, CN 1539856A, CN1789291A, CN1789292A, CN1789290A, WO/2006/063501,200510119401.x etc. use various modes and are loaded, and obtain load type non-metallocene catalysis Agent, but these patents all refer to by the Nonmetallocene organic compound containing transition metal (or for non-metallocene catalyst or Nonmetallocene complex) on the carrier that is carried on that treated or non-metallocene catalyst load capacity is lower or itself and load Body combination is not bery close.

Existing olefin polymerization catalysis patent is mostly based on metallocene catalyst, as US 4808561, US 5240894, CN 1049439、CN 1136239、CN 1344749、CN 1126480、CN1053673、CN 1307594、CN 1130932、 CN 1103069, CN1363537, CN1060179, US574417, EP685494, US4871705 and EP0206794 etc., but It is that these patents are also directed to for the metallocene catalyst containing transition metal to be carried on treated carrier.

Patent EP708116, which is disclosed, first makes the zirconium chloride of gasification contact and bear with carrier at a temperature of 160~450 DEG C Carry, then the zirconium chloride of load reacted to obtain carried metallocene catalyst with the lithium salts of ligand, then by with co-catalysis Agent cooperates and is used for the polymerization of alkene.For the catalyst the problem is that load process requires high temperature, high vacuum is not suitable for work Industry production.

Patent ZL01131136.3 discloses a kind of method for synthesizing carried metallocene catalyst.Wherein make under normal pressure Silica gel mixes in a solvent with IV B group 4 transition metal halide, then directly reacts with ligand anion, thus real in a step The synthesis and load of existing metallocene catalyst.But it is 1: 1 that this method, which requires the molar ratio of transition metal and ligand, and needs to add Enter any proton, such as butyl lithium, and used ligand is the cyclopentadienyl containing cyclopentadienyl group of bridging type or non-bridging type Metal ligand.

The grade of Xiao Yi is discussing " novel Ni (acac) disclosed herein₂/TiCl₄/ L ligand complex catalyst catalyzed ethylene polymerization system The research of standby branched polyethylene " (Zhongshan University's journal: natural science edition, 2003,42 (3): 28), by anhydrous MgCl₂、Ni (acac)₂And L, after being dissolved in tetrahydrofuran-ethyl alcohol mixed solvent, people's silica gel is added to be stirred to react, a certain amount of tetrachloro is added Changing titanium, the reaction was continued, adds a certain amount of Et₂AlCl reaction, drain to obtain catalyst, be thus prepared for be with magnesium chloride-silica gel Carrier, the Ni (acac) modified with alpha-diimine ligand L₂/TiCl₄Composite catalyst.It is poly- using the mono- ethylene of the catalyst Conjunction can obtain branched polyethylene, and it is 4-12 branch number/1000C branched polyethylene that wherein the degree of branching, which is made, in ligand L 2.

Although can be polymerize with the carrier of silica-gel carrier or the complex carrier to contain silica gel as non-metallocene catalyst The good polymer of particle shape is obtained, and can control polymer particle diameter distribution, but the polymerization activity of catalyst is lower, by Contain silica gel in ash, limits the practical use of polymer.

There is document report to handle MgCl using Chloroethyl aluminium₂(THF)₂, and bis cyclopentadienyl zirconium dichloride is loaded, load is thus made Type metallocene catalyst.Its process is: magnesium chloride being dissolved in tetrahydrofuran, at Chloroethyl aluminium after hexane precipitation washing Reason, final load bis cyclopentadienyl zirconium dichloride (EUROPEAN POLYMER JOURNAL, 2005,41,941~947).

Sun Min etc. is in opinion " in-situ reaction preparation CpTi (dbm) Cl disclosed herein₂/MgCl₂It supported catalyst and its urges Change the research of vinyl polymerization " (macromolecule journal, 2004, (1): 138), use Grignard Reagent method to prepare magnesium chloride support, together When be added CpTi (dbm) Cl₂, CpTi (dbm) Cl is prepared with this₂/MgCl₂Supported catalyst.Make the alkylation of catalyst in this way It is completed in a step with supported, greatly reduces the preparation section of catalyst.

Patent CN200510080210.7 discloses supported type vanadium non-metallocene catalyst and the preparation of fabricated in situ Method and application, wherein first reacting to form acyl group naphthols magnesium or beta-diketon magnesium chemical combination with acyl group naphthols or beta-diketon by dialkyl magnesium Object, then reacted with the chloride of tetravalence vanadium, it is formed simultaneously carrier and active catalytic components.

Patent CN200610026765.8 discloses a kind of single active center's Ziegler-Natta olefin polymerization catalyst.It should Catalyst is by magnesium compound using the salicylide for containing coordinating group or substituted salicylaldehyde derivatives as electron donor It is added in (such as magnesium chloride)/tetrahydrofuran solution and passes through pretreated carrier (such as silica gel), metallic compound (such as titanium tetrachloride) And obtained after electron donor processing.Patent CN200610026766.2 is similar therewith, discloses a kind of containing heteroatomic Organic compound and its application in Ziegler-Natta catalyst.

A kind of load type non-metallocene catalyst disclosed in patent CN200710162676.0 and preparation method thereof, is logical It crosses obtained from supported method in situ directly contacts Nonmetallocene ligand with the magnesium compound containing catalytically-active metals.But Contact of the catalytically-active metals with magnesium compound described in it, which refers to, is added to molded magnesium for IV B race metallic compound It closes in object solid (such as magnesium compound solid or magnesium compound solid of modification), such contact cannot accomplish catalytic activity gold Belong to and sufficiently being reacted with magnesium compound, the obtained magnesium compound carrier containing catalytically-active metals necessarily out-phase, is not point It coming into full contact between son and reacts, so that the Nonmetallocene ligand effect for limiting subsequent addition plays completely.

Equally, patent CN200710162667.1 discloses a kind of load type non-metallocene catalyst and preparation method thereof There is similar problem.It is to be matched the compound of catalytically-active metals with containing Nonmetallocene by supported method in situ Obtained from the magnesium compound of body directly contacts.But the contact described in it refer to Nonmetallocene ligand solution is added to it is molded Magnesium compound solid in (such as magnesium compound solid or the magnesium compound solid of modification), such contact cannot accomplish non-cyclopentadienyl Metal ligand is sufficiently reacted with magnesium compound, the magnesium compound carrier of the obtained ligand containing Nonmetallocene necessarily out-phase, Be not it is intermolecular come into full contact with and react, thus limit Nonmetallocene ligand effect complete performance.

Patent CN200910210990.0 discloses a kind of preparation method of load type non-metallocene catalyst, including following The step of step: being dissolved in magnesium compound and Nonmetallocene ligand in solvent in the presence of an alcohol, obtains magnesium compound solution； The step of precipitating reagent is added into the magnesium compound solution, obtains modification carrier；With with selected from IV B race metallic compound The step of chemical treatments handle the modification carrier, obtain the load type non-metallocene catalyst.It can according to disclosure See that its effect of the alcohol of introducing is removed only as the cosolvent of magnesium compound and Nonmetallocene ligand, and then in drying process drying It goes.

Load type non-metallocene catalyst common problem existing in the prior art is that olefin polymerizating activity is low, And in order to improve its activity, it must just assist higher co-catalyst dosage.Moreover, the prior art is due to using silica gel etc. As load carriers, thus it is higher by polymerizeing the ash content of coal in polymer obtained, to limit the reality of polymer Purposes.And the catalyst of magnesium compound load is used to also limit due to the out-phase composition formed in preparation process and distribution Catalyst activity increases substantially.

Therefore, current status is that a kind of load type non-metallocene catalyst is still required, and preparation method is simple, is fitted Industrialized production is closed, and those problems present in prior art load type non-metallocene catalyst can be overcome.

Summary of the invention

The present inventor is on the basis of existing technology by diligent the study found that by using a kind of specific preparation side Method manufactures the load type non-metallocene catalyst, especially concentration thereby through control alcohol in modification carrier, in turn It plays it and is improving the effect in catalyst activity and morphology etc., so that it may solve foregoing problems, and thus complete At the present invention.

In the preparation method of load type non-metallocene catalyst of the invention, any proton (such as this field is not added It is conventional use of those).In addition, not adding electron in the preparation method of load type non-metallocene catalyst of the invention Body (such as the chemical combination such as conventional use of monoesters class, di esters, two ethers, diones and diol-lipid thus in this field Object).Furthermore in the preparation method of load type non-metallocene catalyst of the invention, also without harsh reaction requirement and instead Answer condition.Therefore, the preparation method of the loaded catalyst is simple, and is very suitable for industrialized production.

Specifically, the present invention relates to a kind of preparation methods of load type non-metallocene catalyst, comprising the following steps:

It is dissolved in magnesium compound and Nonmetallocene ligand in solvent in the presence of an alcohol, obtains the step of magnesium compound solution Suddenly；

The magnesium compound solution is dry, or precipitating reagent is added into the magnesium compound solution, it obtains modification and carries The step of body, wherein the content of alcohol described in the modification carrier is 3.0-5.0wt%；With

The modification carrier is handled with the chemical treatments selected from IV B race metallic compound, obtains the non-cyclopentadienyl of the support type The step of metallic catalyst.

The invention further relates to the load type non-metallocene catalysts manufactured by the preparation method, and its alkene homopolymerization/altogether Application in poly-.

Technical effect

The in-situ preparation method simple process of load type non-metallocene catalyst of the invention is feasible, and Nonmetallocene ligand is equal It is distributed in magnesium compound evenly, and the load capacity of Nonmetallocene ligand is adjustable.

Using method for preparing catalyst provided by the invention, it is surprisingly found that due to control stringent during modification carrier drying Certain alcohol content is made and remains, catalytic activity and polymer stacks density are significantly improved, and help needed for polymerization process Catalytic amount is relatively low.

The load type non-metallocene catalyst as prepared by the present invention, copolymerization effect is significant, i.e. the copolymerization of catalyst is living Property be higher than homopolymerization activity, and copolyreaction can be improved the heap density of polymer, that is, improve the particle shape of polymer.

Using load type non-metallocene catalyst provided by the present invention, in the homopolymerization condition that no hydrogen participates in Under, it can polymerize to obtain the higher ultra-high molecular weight polyethylene of molecular weight.

Specific embodiment

Detailed description of the preferred embodiments below, it should be noted however that protection of the invention Range is not limited to these specific embodiments, and but is determined by the appended claims.

In the context of the present invention, unless otherwise defined explicitly or the meaning has exceeded those skilled in the art's Understand range, more than 3 carbon atoms hydrocarbon or hydrocarbon derivative group (such as propyl, propoxyl group, butyl, butane, butylene, butylene Base, hexane etc.) identical meaning when all having when not titled with prefix " just " with titled with prefix " just ".For example, propyl is generally managed Solution is n-propyl, and butyl is generally understood as normal-butyl.

In the context of the present invention, unless otherwise specified, the physics value (such as boiling point) of substance is all room temperature (25 DEG C) and normal pressure (101325Pa) under measured value.

The present invention relates to a kind of preparation methods of load type non-metallocene catalyst, comprising the following steps: makes magnesium compound The step of being dissolved in solvent in the presence of an alcohol with Nonmetallocene ligand, obtaining magnesium compound solution；By the magnesium compound The step of solution is dry, or precipitating reagent is added into the magnesium compound solution, obtains modification carrier, wherein the modification carries The content of alcohol described in body is 3.0-5.0wt%；It is repaired described in the chemical treatments processing of IV B race metallic compound with to be selected from The step of adoring carrier, obtaining the load type non-metallocene catalyst.

It is specifically described below to the step of obtaining the magnesium compound solution.

According to the step, so that magnesium compound and Nonmetallocene ligand is dissolved in solvent appropriate in the presence of an alcohol and (use In the solvent for dissolving the magnesium compound) in, to obtain the magnesium compound solution.

As the solvent, for example C can be enumerated_6-12Aromatic hydrocarbon, halogenated C_6-12Aromatic hydrocarbon, ester and ether equal solvent.Specific ratio Can such as enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene, Ethyl acetate and tetrahydrofuran etc..Wherein, preferably C_6-12Aromatic hydrocarbon and tetrahydrofuran, most preferably tetrahydrofuran.

These solvents can be used alone, and can also be used in mixed way so that arbitrary ratio is a variety of.

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 the alcohol, for example C 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 it is preferred that C_1-30Aliphatic monobasic alcohol Or C_2-8Aliphatic monobasic alcohol, more preferable ethyl alcohol and butanol.In addition, the alcohol optionally can be selected from halogen atom or C_1-6Alkoxy Substituent group replace.

As the C_1-30Fatty alcohol, for example methanol, ethyl alcohol, propyl alcohol, 2- propyl alcohol, butanol, amylalcohol, 2- methyl can be enumerated Amylalcohol, 2- ethylpentanol, 2- hexyl butanol, hexanol and 2-Ethylhexyl Alcohol etc., wherein preferred alcohol, butanol and 2-Ethylhexyl Alcohol.

As the C_6-30Aromatic alcohol, for example benzyl alcohol, benzyl carbinol and methylbenzyl alcohol can be enumerated etc., wherein it is preferred that benzene Ethyl alcohol.

As the C_4-30Alicyclic ring alcohol, for example cyclohexanol, cyclopentanol, Lotka-Volterra circle system, methylcyclopentanol, ethyl ring can be enumerated Amylalcohol, propyl cyclopentanol, methyl cyclohexanol, ethyl cyclohexanol, cyclohexyl alcohol, methyl Lotka-Volterra circle system, ethyl Lotka-Volterra circle system and propyl Lotka-Volterra circle system etc., wherein it is preferred that cyclohexanol and methyl cyclohexanol.

As the alcohol replaced by halogen atom, for example trichlorine methanol, ethapon and three Mecorals can be enumerated etc., In preferred trichlorine methanol.

As the alcohol replaced by alkoxy, for example glycol-ether, ethylene glycol-n-butyl ether and 1- fourth can be enumerated Oxygroup -2- propyl alcohol etc., wherein it is preferred that glycol-ether.

These alcohol can be used alone, and a variety of can also be used in mixed way.In the form of a variety of mixing in use, institute It states ratio between any two kinds of alcohol in alcohol mixture and can be and arbitrarily determine, be not particularly limited.

In order to prepare the magnesium compound solution, the magnesium compound and the Nonmetallocene ligand can be added to by The in the mixed solvent that the solvent and the alcohol are formed is dissolved, or by the magnesium compound and the Nonmetallocene ligand It is added in the solvent, and subsequently or simultaneously addition alcohol is dissolved, but it is not limited to this.

When preparing the magnesium compound solution, the magnesium compound (solid) in terms of magnesium elements rubs with the alcohol You are than being 1: 0.02~4.00, preferably 1: 0.05~3.00, more preferable 1: 0.10~2.50, and the magnesium in terms of magnesium elements The ratio of compound (solid) and the solvent is generally 1mol: 75~400ml, preferably 1mol: 150~300ml, more preferably 1mol: 200~250ml.

According to the present invention, the dosage as the Nonmetallocene ligand so that in terms of Mg element the magnesium compound (Gu Body) with the molar ratio of the Nonmetallocene ligand reach 1: 0.0001-1, preferably 1: 0.0002-0.4, more preferable 1: 0.0008- 0.2, further preferred 1: 0.001-0.1.

To the preparation time of the magnesium compound solution (the i.e. described magnesium compound and the Nonmetallocene ligand dissolution when Between) there is no particular limitation, but generally 0.5~for 24 hours, preferably 4~for 24 hours.In the preparation process, stirring can use to promote Into the dissolution of the magnesium compound and the Nonmetallocene ligand.Any form, such as agitating paddle (revolving speed can be used in the stirring Generally 10~1000rpm) etc..As needed, can promote to dissolve by heating appropriate sometimes.

The magnesium compound is specifically described below.

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

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

Specifically, as the magnesium halide, for example magnesium chloride (MgCl can be enumerated₂), magnesium bromide (MgBr₂), magnesium iodide (MgI₂) and magnesium fluoride (MgF₂) etc., wherein it is preferred that magnesium chloride.

As the Alkoxymagnesium halides, for example methoxy magnesium chloride (Mg (OCH 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), the third oxygen Base 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)、 N-butoxy magnesium iodide (Mg (OC₄H₉) I) and isobutoxy magnesium iodide (Mg (i-OC₄H₉) I) etc., wherein it is preferred that methoxyl group chlorination Magnesium, ethyoxyl magnesium chloride and isobutoxy magnesium chloride.

As the alkoxyl magnesium, for example magnesium methoxide (Mg (OCH 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 it is preferred that magnesium ethylate and isobutoxy magnesium.

As the alkyl magnesium, for example methyl magnesium (Mg (CH can be enumerated₃)₂), magnesium ethide (Mg (C₂H₅)₂), propyl magnesium (Mg(C₃H₇)₂), n-butyl magnesium (Mg (C₄H₉)₂) and isobutyl group magnesium (Mg (i-C₄H₉)₂) etc., wherein it is preferred that magnesium ethide and normal-butyl Magnesium.

As the alkyl halide magnesium, for example methyl-magnesium-chloride (Mg (CH can be enumerated₃) Cl), ethylmagnesium chloride (Mg (C₂H₅) Cl), propyl 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 magnesium bromide (Mg (C₃H₇)Br)、 Normal-butyl magnesium bromide (Mg (C₄H₉) Br), selenium alkynide (Mg (i-C₄H₉) Br), methylpyridinium iodide magnesium (Mg (CH₃) I), ethyl iodide Change magnesium (Mg (C₂H₅) I), propyl magnesium iodide (Mg (C₃H₇) I), normal-butyl magnesium iodide (Mg (C₄H₉) I) and isobutyl group magnesium iodide (Mg (i-C₄H₉) I) etc., wherein it is preferred that methyl-magnesium-chloride, ethylmagnesium chloride and isobutyl group magnesium chloride.

As the alkyl alkoxy magnesium, for example methyl methoxy base magnesium (Mg (OCH can be enumerated₃)(CH₃)), methylethoxy Base magnesium (Mg (OC₂H₅)(CH₃)), methyl propoxyl group magnesium (Mg (OC₃H₇)(CH₃)), methyl n-butoxy magnesium (Mg (OC₄H₉) (CH₃)), methyl tert-butyl oxygroup 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 oxygroup magnesium (Mg (i-OC₄H₉)(C₂H₅)), propylmethoxy magnesium (Mg (OCH₃)(C₃H₇)), propyl ethoxy Base magnesium (Mg (OC₂H₅)(C₃H₇)), propyl propoxyl group magnesium (Mg (OC₃H₇)(C₃H₇)), propyl n-butoxy magnesium (Mg (OC₄H₉) (C₃H₇)), propyl 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)), isobutyl Base n-butoxy magnesium (Mg (OC₄H₉)(i-C₄H₉)) and isobutyl group isobutoxy magnesium (Mg (i-OC₄H₉)(i-C₄H₉)) etc., wherein excellent Select butyl magnesium ethylate.

These magnesium compounds can be used alone, and a variety of can also be used in mixed way, be not particularly limited.

In the form of a variety of mixing in use, between any two kinds of magnesium compounds in the magnesium compound mixture Molar ratio is such as 0.25~4: 1, preferably 0.5~3: 1, more preferable 1~2: 1.

According to the present invention, term " Nonmetallocene complex " is a kind of single centre alkene for metallocene catalyst Polymerized hydrocarbon catalyst, without containing cyclopentadienyl groups such as luxuriant ring, fluorenes ring or indenes ring or derivatives thereof in structure, and with co-catalysis (therefore agent (such as those described below) can show that the active metallo-organic compound of olefinic polymerization catalysis when combining The Nonmetallocene complex is also sometimes referred to as non-metallocene olefin polymerization complex).The compound includes central metal Atom and at least one with the multidentate ligand in conjunction with coordinate bond, (preferably tridentate ligand or more is matched with the central metal atom Body), and term " Nonmetallocene ligand " is multidentate ligand above-mentioned.

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

According to the present invention, group A, D and E in the compound (coordination group) pass through the coordination atom contained by it Contained by the IV B race metallic compound used in (such as the hetero atoms such as N, O, S, Se and P) and the present invention as chemical treatments IV B race's metallic atom occurs complexation reaction and forms coordinate bond, is consequently formed using IV B race's metallic atom as center metal original The complex (Nonmetallocene complex i.e. of the present invention) of sub- M.

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

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

In all of above chemical structural formula,

Q is 0 or 1；

D is 0 or 1；

A be 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 are 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 are respectively coordination atom；

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

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

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

Y is selected from nitrogen-containing group, oxygen-containing group, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se and P are each From for coordination atom；

Z is selected from nitrogen-containing group, oxygen-containing group, sulfur-containing group, group containing seleno, phosphorus-containing groups or cyano (- CN), such as can be with 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 are respectively coordination atom；

→ represent singly-bound or double bond；

Represent covalent bond or ionic bond.

R¹To R⁴、R⁶To R²¹It is each independently selected from hydrogen, C₁-C₃₀Alkyl, substituted C₁ -C₃₀Alkyl is (wherein preferably halogenated Alkyl, such as-CH₂Cl and-CH₂CH₂) or safing function group Cl.R²²To R³⁶、R³⁸And R³⁹It is each independently selected from hydrogen, C₁- C₃₀Alkyl or substituted C₁-C₃₀Alkyl (wherein preferred halohydrocarbyl, such as-CH₂Cl and-CH₂CH₂Cl).Above-mentioned group is to each other It can be the same or different, 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 R²⁴Or R²⁵With R²⁶Etc. can combine togather bonding or Cyclization, is preferably formed as aromatic ring, such as unsubstituted phenyl ring or by 1-4 C₁-C₃₀Alkyl or substituted C₁-C₃₀Alkyl (its In preferred halohydrocarbyl, such as-CH₂Cl and-CH₂CH₂Cl) the phenyl ring replaced.

R⁵Lone pair electrons, hydrogen, C on nitrogen₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl, sulfur-containing group, contains oxygen-containing group Nitrogen groups contain seleno group or phosphorus-containing groups.Work as R⁵For oxygen-containing group, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups When, R⁵In N, O, S, P and Se can be used as coordination and (be coordinated with the central metal atom M) with atom.

In the context of the present invention, the safing function group can such as be enumerated selected from halogen, oxygen-containing group, contain Nitrogen groups, germanic group, sulfur-containing group, contain tin group, C at silicon-containing group₁-C₁₀Ester group or nitro (- NO₂) at least one etc., It but does not include usually C₁- C₃₀Alkyl and substituted C₁-C₃₀Alkyl.

In the context of the present invention, it is limited by the chemical structure of multidentate ligand of the present invention, the safing function Group has the following characteristics that

(1) complexation process of described group A, D, E, F, Y or Z Yu the central metal atom M are not interfered, and

(2) it is lower than described A, D, E, F, Y and Z group with the coordination ability of the central metal atom M, and does not replace These groups have coordination with the central metal atom M's.

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

In the context of the present invention,

The halogen is selected from F, Cl, Br or I.The nitrogen-containing group is selected from-NR²³R²⁴、 -T-NR²³R²⁴Or-N (O) R²⁵R²⁶.The phosphorus-containing groups are selected from-PR²⁸R²⁹、 -P(O)R³⁰R³¹Or-P (O) R³²(OR³³).The oxygen-containing group choosing From hydroxyl ,-OR³⁴With-T-OR³⁴.The sulfur-containing group is selected from-SR³⁵、-T-SR³⁵、-S(O)R³⁶Or-T-SO₂R³⁷.It is described to contain selenium Group is selected from-SeR³⁸、-T-SeR³⁸、-Se(O)R³⁹Or-T-Se (O) R³⁹.The group T is selected from C₁-C₃₀Alkyl is substituted C₁-C₃₀Alkyl.The R³⁷Selected from hydrogen, C₁-C₃₀Alkyl or substituted C₁-C₃₀Alkyl.

In the context of the present invention, the C₁-C₃₀Alkyl is selected from C₁-C₃₀Alkyl (preferably C₁-C₆Alkyl, such as isobutyl Base), C₇-C₃₀Alkaryl (such as tolyl, xylyl, diisobutyl phenyl etc.), C₇-C₃₀Aralkyl (such as benzyl), C₃- C₃₀Cyclic alkyl, C₂-C₃₀Alkenyl, C₂-C₃₀Alkynyl, C₆-C₃₀Aryl (such as phenyl, naphthalene, anthryl etc.), C₈-C₃₀Condensed ring radical Or C₄-C₃₀Heterocycle, wherein the heterocycle contains the 1-3 hetero atoms for being selected from nitrogen-atoms, oxygen atom or sulphur atom, such as pyrrole Piperidinyl, pyrrole radicals, furyl or thienyl etc..

According to the present invention, in the context of the present invention, described according to the concrete condition of the related group in conjunction with it C₁-C₃₀Alkyl is sometimes referred to as C₁-C₃₀Hydrocarbon diyl (bivalent group, or referred to as C₁-C₃₀Alkylene) or C₁-C₃₀Three base (three of hydrocarbon Valence group), this is obvious to those skilled in the art.

In the context of the present invention, the substituted C₁-C₃₀Alkyl is referred 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 also optionally include R⁵) do not have with the complexation process of central metal atom M (i.e. aforementioned IV B race metallic atom) There is substantive interference；In other words, it is limited by the chemical structure of ligand of the present invention, these substituent groups have no ability to or without machine Meeting (for example being influenced by steric hindrance etc.) and IV B race's metallic atom occur complexation reaction and form coordinate bond.It is general and Speech, the inert substituent are selected from halogen or C₁-C₃₀Alkyl (preferably C₁-C₆Alkyl, such as isobutyl group).

In the context of the present invention, the silicon-containing group is selected from-SiR⁴²R⁴³R⁴⁴Or-T-SiR⁴⁵；The germanic group choosing From-GeR⁴⁶R⁴⁷R⁴⁸Or-T-GeR⁴⁹；It is described to be selected from-SnR containing tin group⁵⁰R⁵¹R⁵²、-T-SnR⁵³Or-T-Sn (O) R⁵⁴；And institute State R⁴²To R⁵⁴It is each independently selected from hydrogen, C above-mentioned₁-C₃₀Alkyl or substituted C above-mentioned₁-C₃₀Alkyl, above-mentioned group is each other Between can be the same or different, wherein adjacent group can combine togather bonding or cyclization.The wherein definition of group T Ditto.

As the Nonmetallocene ligand, for example following compound can be enumerated:

The Nonmetallocene ligand is preferably selected from following compound:

The Nonmetallocene ligand is further preferably selected from following compound:

The Nonmetallocene ligand is more preferably selected from following compound:

These Nonmetallocene ligands can be used alone, or is applied in combination with arbitrary ratio a variety of.

According to the present invention, the Nonmetallocene ligand is not usually used as electronic donor compound in this field Diether compounds.

The Nonmetallocene ligand can be manufactured according to any method well known by persons skilled in the art.About its system Make the particular content of method, such as reference can be made to WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 Full text of these documents is introduced as reference with regard to this Deng, this specification.

The magnesium compound solution is dry, or precipitating reagent is added into the magnesium compound solution, it obtains modification and carries Body.

The precipitating reagent is specifically described below.

According to the present invention, term " precipitating reagent " uses the common concept in this field, refers to can reduce solute (such as institute State magnesium compound) in the solubility in its solution and and then chemical inertness liquid that it is precipitated in solid form from the solution State.

According to the present invention, as the precipitating reagent, for example can enumerate is poor solvent for the magnesium compound, It and is the solvent of good solvent for the solvent for dissolving the magnesium compound, for example alkane, cycloalkanes can be enumerated Hydrocarbon, halogenated alkane and halogenated cycloalkane.

As the alkane, for example pentane, hexane, heptane, octane, nonane and decane can be enumerated etc., wherein it is preferred that oneself Alkane, heptane and decane, most preferably hexane.

As the cycloalkane, for example hexamethylene can be enumerated, pentamethylene, cycloheptane, cyclodecane and cyclononane etc. are optimal Ring selection hexane.

As the halogenated alkane, for example methylene chloride, dichloro hexane, two chloroheptanes, chloroform, trichlorine can be enumerated Ethane, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane and three bromobutane etc..

As the halogenated cycloalkane, for example chlorocyclopentane, chlorocyclohexane, chloro cycloheptane, chloro can be enumerated Cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo cycloheptane, bromo cyclooctane, bromo Cyclononane and bromo cyclodecane etc..

These precipitating reagents can be used alone, and can also be used in mixed way so that arbitrary ratio is a variety of.

The adding manner of precipitating reagent can be to be added at one time or be added dropwise, and preferably be added at one time.In the precipitation process In, it can use stirring to promote dispersion of the precipitating reagent in the magnesium compound solution, and be conducive to the final of solid product Precipitating.Any form, such as agitating paddle (revolving speed is generally 10~1000rpm) etc. can be used in the stirring.

To the dosage of the precipitating reagent, there is no particular limitation, but it is general by volume, the precipitating reagent be used to dissolve The ratio of the solvent of the magnesium compound is 1: 0.2~5, preferably 1: 0.5~2, more preferable 1: 0.8~1.5.

To the temperature of the precipitating reagent, also there is no particular limitation, but generally preferably room temperature.Moreover, the precipitation process is general It is also preferred that carrying out at normal temperature.

Completely after precipitating, solid product obtained is filtered, optionally washing and drying, can be obtained the modification Carrier.The method being filtered, washed and dried is not particularly limited, can according to need using this field routine Those of use.

As needed, the washing is general carries out 1~6 time, preferably 2~3 times.Wherein, washer solvent it is preferable to use with The identical solvent of precipitating reagent, however, you can also not same.

According to the present invention, by the way that the magnesium compound solution is dry, or by the solid product filtering (and optionally Washing) it is dried later, the content of alcohol described in the modification carrier is controlled as 3.0-5.0wt%, preferably 3.5- 4.5wt%.

According to the present invention, the drying can be carried out using conventional method, such as inert gas seasoning, boulton process Or heating under vacuum seasoning, preferably inert gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum are dry Dry method.

According to the present invention, the drying mode (including drying temperature, dry vacuum degree and drying time) is with the modification The alcohol content of carrier meets aforementioned claim of the present invention and is limited.For example, by the magnesium compound solution lower than the solvent boiling point It is 10-30 DEG C preferably low at a temperature of 5-50 DEG C, under the vacuum of absolute pressure 2-100mBar, preferably 5-50mBar, dry 2- 30h, preferably 4-12h, then from the solvent boiling point to 30 DEG C higher than the solvent boiling point at a temperature of, preferably from described molten Agent boiling point is at a temperature of 20 DEG C higher than the solvent boiling point, under the vacuum of absolute pressure 2-100mBar, preferably 5- 50mBar, dry 1-20h, preferably 2-8h, thus to obtain the modification carrier.Alternatively, being added into the magnesium compound solution Precipitating reagent, by sediment obtained (optionally after wash) 5-50 DEG C lower than the solvent boiling point at a temperature of, preferably Low 10-30 DEG C, under the vacuum of absolute pressure 2-100mBar, then preferably 5-50mBar, dry 2-30h, preferably 4-12h exist From the solvent boiling point at a temperature of 30 DEG C higher than the solvent boiling point, preferably from the solvent boiling point to than the solvent At a temperature of high 20 DEG C of boiling point, under the vacuum of absolute pressure 2-100mBar, preferably 5-50mBar, dry 1-20h, preferably 2- 8h, thus to obtain the modification carrier.

Then, the modification carrier is handled with the chemical treatments selected from IV B race metallic compound, thus to obtain this hair Bright load type non-metallocene catalyst.

According to the present invention, by being chemically treated with the chemical treatments to the modification carrier, can make described Chemical treatments react with Nonmetallocene ligand contained in the modification carrier, thus the non-cyclopentadienyl gold of in-situ preparation on carrier Metal complex (supported reaction in situ), thus to obtain load type non-metallocene catalyst of the invention.

The chemical treatments are specifically described below.

According to the present invention, using IV B race's metallic compound as the chemical treatments.

As IV B race metallic compound, for example IV B race metal halide, IV B race metal alkyl can be enumerated Compound, IV B race metal alkoxide, IV B race's metal alkyl halides and IV B race metal alkoxide halide.

As IV B race metal halide, IV B race metal alkyl compound, IV B race metal alcoxyl Based compound, IV B race's metal alkyl halides and IV B race metal alkoxide halide, for example, can enumerate as The compound of logical formula (IV) structure down:

M(OR¹)_mX_nR² _4-m-n (IV)

Wherein:

M is 0,1,2,3 or 4；

N is 0,1,2,3 or 4；

M is IV B race metal, such as titanium, zirconium and hafnium etc. in the periodic table of elements；

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

R¹And R²It is each independently selected from C_1-10Alkyl, such as methyl, ethyl, propyl, normal-butyl, isobutyl group etc., R¹And R² It may be the same or different.

Specifically, as IV B race metal halide, for example titanium tetrafluoride (TiF can be enumerated₄), four chlorinations Titanium (TiCl₄), titanium tetrabromide (TiBr₄), titanium tetra iodide (TiI₄)；

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

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

As IV B race metal alkyl compound, for example tetramethyl titanium (Ti (CH 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)), it is 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), two isobutyls Base 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 normal-butyl zirconium (Zr (CH₃)₃(C₄H₉)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH₃CH₂)(C₄H₉)₃), two positive fourths Base 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), two isobutyls Base 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 normal-butyl hafnium (Hf (CH₃)₃(C₄H₉)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH₃CH₂)(C₄H₉)₃), two positive fourths Base diethyl hafnium (Hf (CH₃CH₂)₂(C₄H₉)₂), triethyl group normal-butyl hafnium (Hf (CH₃CH₂)₃(C₄H₉)) etc..

As IV B race metal alkoxide, for example titanium tetramethoxide (Ti (OCH can be enumerated₃)₄), tetrem Oxygroup titanium (Ti (OCH₃CH₂)₄), four isobutoxy titanium (Ti (i-OC₄H₉)₄), four titanium n-butoxides (Ti (OC₄H₉)₄), three ethoxies Ylmethoxy titanium (Ti (OCH₃)(OCH₃CH₂)₃), diethoxy dimethoxy titanium (Ti (OCH₃)₂(OCH₃CH₂)₂), trimethoxy Ethanolato-titanium (Ti (OCH₃)₃(OCH₃CH₂)), three isobutoxy methoxyl group titanium (Ti (OCH₃)(i-OC₄H₉)₃), two isobutoxies two Methoxyl group titanium (Ti (OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutoxy titanium (Ti (OCH₃)₃(i-OC₄H₉)), three isobutoxies Ethanolato-titanium (Ti (OCH₃CH₂)(i-OC₄H₉)₃), two isobutoxy diethoxy titanium (Ti (OCH₃CH₂)₂(i-OC₄H₉)₂), three second Oxygroup isobutoxy titanium (Ti (OCH₃CH₂)₃(i-OC₄H₉)), three n-butoxy methoxyl group titanium (Ti (OCH₃)(OC₄H₉)₃), two just Butoxy dimethoxy titanium (Ti (OCH₃)₂(OC₄H₉)₂), trimethoxy titanium n-butoxide (Ti (OCH₃)₃(OC₄H₉)), three positive fourths Oxymethoxy titanium (Ti (OCH₃CH₂)(OC₄H₉)₃), two n-butoxy diethoxy titanium (Ti (OCH₃CH₂)₂(OC₄H₉)₂), three second Oxygroup 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 Oxygroup zirconium (Zr (OCH₃CH₂)₂(i-OC₄H₉)₂), triethoxy isobutoxy zirconium (Zr (OCH₃CH₂)₃(i-OC₄H₉)), three positive fourths Oxymethoxy zirconium (Zr (OCH₃)(OC₄H₉)₃), two n-butoxy dimethoxy zirconium (Zr (OCH₃)₂(OC₄H₉)₂), trimethoxy N-butoxy zirconium (Zr (OCH₃)₃(OC₄H₉)), three n-butoxy methoxyl group zirconium (Zr (OCH₃CH₂)(OC₄H₉)₃), two n-butoxies Diethoxy 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 IV B race metal alkyl halides, for example trimethyl ammonia chloride titanium (TiCl (CH can be enumerated₃)₃), three Ethylmercury chloride titanium (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 two Titanium chloride (TiCl₂(i-C₄H₉)₂), three n-butylmagnesium chloride titanium (TiCl (C₄H₉)₃), methyl titanium trichloride (Ti (CH₃)Cl₃), ethyl Titanium trichloride (Ti (CH₃CH₂)Cl₃), isobutyl group titanium trichloride (Ti (i-C₄H₉)Cl₃), normal-butyl titanium trichloride (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 IV B race metal alkoxide halide, for example trimethoxy titanium chloride (TiCl can be enumerated (OCH₃)₃), triethoxy titanium chloride (TiCl (OCH₃CH₂)₃), three isobutoxy titanium chloride (TiCl (i-OC₄H₉)₃), three positive fourths Oxygroup titanium chloride (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 titanium trichloride (Ti (OCH₃CH₂)Cl₃), isobutoxy titanium trichloride (Ti (i-C₄H₉)Cl₃), nbutoxytitanium trichloride (Ti (OC₄H₉)Cl₃)；

Trimethoxy titanium bromide (TiBr (OCH₃)₃), triethoxy titanium bromide (TiBr (OCH₃CH₂)₃), three isobutoxies Titanium bromide (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 isobutoxies Zirconium chloride (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 isobutoxies Zirconium bromide (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 isobutoxies Hafnium chloride (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 IV B race metallic compound, preferably IV B race metal halide, more preferable TiCl₄、TiBr₄、 ZrCl₄、ZrBr₄、HfCl₄And HfBr₄, most preferably TiCl₄And ZrCl₄。

These IV B race metallic compounds can be used alone, or is applied in combination with arbitrary ratio a variety of.

When the chemical treatments are at normal temperature liquid, the chemistry directly can be carried out using the chemical treatments Processing reaction.When the chemical treatments are at normal temperature solid-state, in order to measure with it is easy to operate for the sake of, preferably with solution Form uses the chemical treatments.It certainly, can also sometimes according to needs when the chemical treatments are at normal temperature liquid To use the chemical treatments as a solution, it is not particularly limited.

When preparing the solution of the chemical treatments, to used solvent at this time, there is no particular limitation, as long as its The chemical treatments can be dissolved and do not destroy the existing carrier of (such as dissolution) described magnesium compound or the modification carrier Structure.

Specifically, C can be enumerated_5-12Alkane, C_5-12Cycloalkane, halogenated C_5-12Alkane and halogenated C_5-12Cycloalkane etc., than Pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, pentamethylene, hexamethylene, cycloheptane, ring can such as be enumerated Octane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro hendecane, chloro ten Dioxane and chlorocyclohexane etc., wherein it is preferred that pentane, hexane, decane and hexamethylene, most preferably hexane.

These solvents can be used alone, or is applied in combination with arbitrary ratio a variety of.

In addition, to concentration of the chemical treatments in its solution, there is no particular limitation, and it is appropriate to can according to need Selection is reacted as long as it can be realized with the chemical treatments of predetermined amount to carry out the chemical treatment.Such as preceding institute It states, if chemical treatments are liquid, the processing can be directly carried out using chemical treatments, but can also be adjusted It is used after the solution of chemical treatments is made.

In general, molar concentration of the chemical treatments in its solution is usually set to 0.01~1.0mol/L, But it is not limited to this.

It as carrying out the chemically treated method, for example can enumerate, using solid chemical processing agent (such as tetrachloro Change zirconium) in the case where, the solution of the chemical treatments is prepared first, is then added into the modification carrier to be processed The chemical treatments of (being preferably added dropwise) predetermined amount；Using liquid chemical inorganic agent (such as titanium tetrachloride), Directly (but or after being prepared into solution) chemical treatments of predetermined amount can be added and (be preferably added dropwise) wait locate In the modification carrier of reason, and react chemical treatment under the reaction temperature of -30~60 DEG C (preferably -20~30 DEG C) (when necessary by stirring) progress 0.5~for 24 hours, then preferably 1~8h, more preferable 2~6h are filtered, wash and dry i.e. It can.

According to the present invention, described be filtered, washed and dried can be carried out using conventional method, and wherein washer solvent can be with Identical solvent used when using with the dissolution chemical treatments.The washing generally carries out 1~8 time, preferably 2~6 times, optimal It selects 2~4 times.

According to the present invention, the dosage as the chemical treatments so that in terms of Mg element the magnesium compound (Gu Body) with the molar ratios of chemical treatments in terms of IV B race metal (such as Ti) element reach 1: 0.01-1, preferably 1: 0.01-0.50, more preferable 1: 0.10-0.30.

A special embodiment according to the present invention, the preparation method of load type non-metallocene catalyst of the invention is also It is included in front of handling the modification carrier using the chemical treatments, with selected from aikyiaiurnirsoxan beta, alkyl aluminum or any combination thereof Help chemical treatments pre-process the modification carrier the step of (pre-treatment step).Then, according still further to it is aforementioned identical Mode carry out the chemical treatment with the chemical treatments, only by the modification carrier replace with it is described through pretreatment Modification carrier.

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

According to the present invention, chemical treatments are helped as described, for example aikyiaiurnirsoxan beta and alkyl aluminum can be enumerated.

As the aikyiaiurnirsoxan beta, for example linear alumoxanes shown in the following general formula (I): (R) (R) Al- (Al can be enumerated (R)-O)_nCyclic aluminoxane shown in-O-Al (R) (R) and the following general formula (II) :-(Al (R)-O-)_n+2-。

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

As the aikyiaiurnirsoxan beta, preferably methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, Further preferred methylaluminoxane and isobutyl aluminium alkoxide.

These aikyiaiurnirsoxan betas can be used alone, or is applied in combination with arbitrary ratio a variety of.

As the alkyl aluminum, for example logical formula (III) compound represented as follows can be enumerated:

Al(R)₃ (III)

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

Specifically, as the alkyl aluminum, for example trimethyl aluminium (Al (CH can be enumerated₃)₃), triethyl aluminum (Al (CH₃CH₂)₃), tri-propyl aluminum (Al (C₃H₇)₃), triisobutyl aluminium (Al (i-C₄H₉)₃), three n-butylaluminums (Al (C₄H₉)₃), three Isopentyl aluminium (Al (i-C₅H₁₁)₃), three n-pentyl aluminium (Al (C₅H₁₁)₃), three hexyl aluminium (Al (C₆H₁₃)₃), three isohesyl aluminium (Al (i-C₆H₁₃)₃), diethylmethyl aluminium (Al (CH₃)(CH₃CH₂)₂) and dimethyl ethyl aluminium (Al (CH₃CH₂)(CH₃)₂) etc., In preferably trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.

These alkyl aluminums can be used alone, or is applied in combination with arbitrary ratio a variety of.

According to the present invention, chemical treatments are helped as described, it is possible to use only the aikyiaiurnirsoxan beta, it can also be only with described Alkyl aluminum, but any mixture of the aikyiaiurnirsoxan beta and the alkyl aluminum can also be used.Moreover, to each component in the mixture Ratio there is no particular limitation, can according to need any selection.

According to the present invention, described that chemical treatments is helped usually to use as a solution.Chemistry is helped described in the preparation When the solution of inorganic agent, to used solvent at this time, there is no particular limitation, as long as it, which can dissolve this, helps chemical treatments And do not destroy the existing carrier structure of (such as dissolution) carrier.

Specifically, as the solvent, for example C can be enumerated_5-12Alkane and halogenated C_5-12Alkane etc., for example can lift Pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, hexamethylene, chloro-pentane, chloro-hexane, chloro heptan out Alkane, chloro octane, chloro nonane, chloro decane, chloro hendecane, chlorinated dodecane and chlorocyclohexane etc., wherein it is preferred that penta Alkane, hexane, decane and hexamethylene, most preferably hexane.

In addition, to the concentration for helping chemical treatments in its solution, there is no particular limitation, can according to need suitable Work as selection, as long as it can be realized to help chemical treatments to carry out the pretreatment described in predetermined amount.

It as carrying out the pretreated method, for example can enumerate, prepare described help the molten of chemical treatments first Liquid, then -30~60 DEG C (preferably -20~30 DEG C) at a temperature of, the pretreated modification of chemical treatments is helped described in quasi- (being preferably added dropwise) described help metered in carrier is chemically treated agent solution (containing chemical treatments are helped described in predetermined amount), or Person helps the chemical treatment agent solution amount of falling into a trap that the modification carrier is added to described, and reaction mixture is consequently formed, make its reaction 1~ 8h, preferably 2~6h, most preferably 3~4h (when necessary by stirring).Then, pretreatment product obtained was passed through Filter, washing (1~6 time, preferably 1~3 time) and optionally drying, and separated from the reaction mixture, alternatively, can also be with Subsequent reaction step is directly used in the form of mixed liquor without the separation.At this point, due in the mixed liquor Contain a certain amount of solvent, it is possible to accordingly reduce solvent usage involved in the subsequent reactions step.

According to the present invention, as the dosage for helping chemical treatments so that in terms of Mg element the magnesium compound (Gu Body) in terms of Al element described in help the molar ratio of chemical treatments to reach 1: 0-1.0, preferably 1: 0-0.5, more preferable 1: 0.1- 0.5。

Known to those skilled in the art to be, aforementioned all method and steps are preferably in the item of substantially anhydrous and oxygen-free It is carried out under part.Substantially anhydrous and oxygen-free mentioned here refers to that the content of water and oxygen is continuously less than 10ppm in system.Moreover, Load type non-metallocene catalyst of the invention usually requires micro-positive pressure in confined conditions after preparation and saves backup.

According to the present invention, the dosage as the solvent for dissolving the magnesium compound, so that the magnesium compound The ratio of (solid) and the solvent reaches 1mol: 75~400ml, preferably 1mol: 150~300ml, more preferable 1mol: 200~ 250ml。

According to the present invention, the use as the alcohol being used cooperatively with the solvent for dissolving the magnesium compound Amount, so that the molar ratio of the magnesium compound (solid) and the alcohol in terms of Mg element reaches 1: 0.02~4.00, preferably 1: 0.05~3.00, more preferable 1: 0.10~2.50.

According to the present invention, the dosage as the precipitating reagent so that the precipitating reagent with for dissolving the magnesium compound The solvent volume ratio be 1: 0.2~5, preferably 1: 0.5~2, more preferable 1: 0.8~1.5.

In one embodiment, the invention further relates to the preparation method systems by load type non-metallocene catalyst above-mentioned 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 methods, wherein with the present invention Load type non-metallocene catalyst as catalyst for olefines polymerizing, make alkene homopolymerization or copolymerization.

For the alkene homopolymerization/copolymerization method according to the present invention, other than the following content particularly pointed out, The content (such as polymerization reactor, alkene dosage, catalyst and addition manner of alkene etc.) that he does not explain, can directly fit With those of conventionally known in the art, it is not particularly limited, the description thereof will be omitted herein.

Homopolymerization/copolymerization method according to the present invention, using load type non-metallocene catalyst of the invention as major catalyst, with Selected from one of aikyiaiurnirsoxan beta, alkyl aluminum, halogenated alkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt or it is a variety of be co-catalysis Agent makes alkene homopolymerization or copolymerization.

The adding manner of major catalyst and co-catalyst into polymerization reaction system, which can be, first adds major catalyst, then again Co-catalyst is added, or co-catalyst is first added, then add major catalyst or the two first contact mix after together It is added, or is added simultaneously respectively.When major catalyst and co-catalyst are separately added into both can in same Feed lines according to Secondary addition can also sequentially add in multichannel Feed lines, and the two should select multichannel Feed lines respectively while when being added. For continous way polymerization reaction, preferably multichannel Feed lines are continuously added to simultaneously, and for intermittence type polymerization reaction, It is preferred that the two is added in same Feed lines together after first mixing, or co-catalyst is first added in same Feed lines, Then major catalyst is added.

According to the present invention, to the reactive mode of the alkene homopolymerization/copolymerization method, there is no particular limitation, can be using this Field is those of known, for example can enumerate slurry process, emulsion method, solwution method, substance law and vapor phase method etc., wherein preferred slurries Method and vapor phase method.

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

Specifically, as the C₂~C₁₀Monoolefine, for example ethylene, propylene, 1- butylene, 1- hexene, 1- can be enumerated Heptene, 4-methyl-1-pentene, 1- octene, 1- decene, 1- hendecene, 1- laurylene and styrene etc.；As the cyclic annular alkene Hydrocarbon, for example 1- cyclopentene and norbornene can be enumerated etc.；As the diolefin, for example Isosorbide-5-Nitrae-butadiene, 2 can be enumerated, 5- pentadiene, 1,6- hexadiene, norbornadiene and 1,7- octadiene etc.；And as other described ethylenic bond unsaturation chemical combination Object, for example vinylacetate and (methyl) acrylate etc. can be enumerated.Wherein, the homopolymerization of optimal ethylene or ethylene and third The copolymerization of alkene, 1- butylene or 1- hexene.

According to the present invention, homopolymerization refers to a kind of only polymerization of the alkene, and is copolymerized and refers to the two or more alkene Polymerization between hydrocarbon.

According to the present invention, the co-catalyst is selected from aikyiaiurnirsoxan beta, alkyl aluminum, halogenated alkyl aluminium, boron fluothane, boron alkyl and alkane Base boron ammonium salt, wherein it is preferred that aikyiaiurnirsoxan beta and alkyl aluminum.

As the aikyiaiurnirsoxan beta, for example linear alumoxanes shown in the following general formula (I-1): (R) (R) Al- (Al can be enumerated (R)-O)_nCyclic aluminoxane shown in-O-Al (R) (R) and the following general formula (II-1) :-(Al (R)-O-)_n+2-。

As the aikyiaiurnirsoxan beta, preferably methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, Further preferred methylaluminoxane and isobutyl aluminium alkoxide, and most preferable aikyiaiurnirsoxan beta.

As the alkyl aluminum, for example following general formula (III-1) compound represented can be enumerated:

Al(R)₃ (III-1)

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

As the halogenated alkyl aluminium, the boron fluothane, the boron alkyl and the boron alkyl ammonium salt, can directly use It is those of commonly used in the art, it is not particularly limited.

In addition, according to the present invention, the co-catalyst can be used alone, also can according to need arbitrarily to compare A variety of co-catalysts above-mentioned are applied in combination in example, are not particularly limited.

According to the present invention, according to the difference of the reactive mode of the alkene homopolymerization/copolymerization method, it is sometimes desirable to use polymerization Use solvent.

As the solvent for polymerization, this field can be used and those of routinely used when carrying out alkene homopolymerization/copolymerization, It is not particularly limited.

As the solvent for polymerization, for example C can be enumerated_4-10Alkane (such as butane, pentane, hexane, heptane, octane, Nonane or decane etc.), halogenated C_1-10Alkane (such as methylene chloride), aromatic hydrocarbon solvent (such as toluene and dimethylbenzene), ethers Solvent (such as ether or tetrahydrofuran), esters solvent (such as ethyl acetate) and ketones solvent (such as acetone) etc..Wherein, excellent Choosing uses hexane as the solvent for polymerization.

These solvent for polymerization can be used alone, or is applied in combination with arbitrary ratio a variety of.

According to the present invention, the polymerization pressure of the alkene homopolymerization/copolymerization method is generally 0.1~10MPa, preferably 0.1~4MPa, more preferable 1~3MPa, but is not limited thereto.According to the present invention, polymeric reaction temperature be generally -40 DEG C~ 200 DEG C, preferably 10 DEG C~100 DEG C, more preferable 40 DEG C~90 DEG C, but is not limited thereto.

In addition, according to the present invention, the alkene homopolymerization/copolymerization method can carry out under the conditions of having existing for hydrogen, It is carried out under the conditions of can be existing for no hydrogen.In case of presence, the partial pressure of hydrogen can be the polymerization reaction pressure The 0.01%~99% of power, preferably 0.01%~50 %, but is not limited thereto.

According to the present invention, when carrying out the alkene homopolymerization/copolymerization method, the co-catalyst in terms of aluminium or boron with The molar ratio of the load type non-metallocene catalyst of IV B race metal meter is generally 1: 1~1000, preferably 1: 1~500, more It is preferred that 1: 10~500, but is not limited thereto.

Embodiment

The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.

(unit is g/cm to polymer stacks density³) measurement referring to chinese national standard GB 1636-79 carry out.

The content of IV B race metal (such as Ti) and Mg element is surveyed using ICP-AES method in load type non-metallocene catalyst Fixed, the content of Nonmetallocene ligand is measured using elemental microanalysis method.

The polymerization activity of catalyst calculates in accordance with the following methods: after polymerization reaction terminates, by the polymerization in reaction kettle Product is filtered and is dried, and then weighs the quality of the polymerizate, with the polymerizate quality divided by the non-cyclopentadienyl of support type used The ratio of the quality of metallic catalyst come indicate the catalyst polymerization activity (unit be kg polymer/g catalyst or kg polymerization Object/gCat).

The viscosity average molecular weigh of polymer calculates in accordance with the following methods: according to standard ASTM D4020-00, using high temperature dilution (capillary inner diameter 0.44mm, constant temperature bath medium are No. 300 silicone oil to type Ubbelohde viscometer method, and dilution is decahydronaphthalene with solvent, are surveyed Determining temperature is 135 DEG C) inherent viscosity of the measurement polymer, the viscous of the polymer then, which is calculated, according to following formula divides equally Son amount Mv.

Mv=5.37 × 10⁴×[η]^1.37

Wherein, η is inherent viscosity.

The measurement of alcohol content is as follows in carrier: carrying out quantitative analysis using capillary gas chromatography, instrument is adopted With Agilent 6890N type gas chromatograph, it is equipped with autosampler, flame ionization ditector (FID)；Chromatographic column is DB-1 (30m × 0.32mm × 0.25 μm), gas-chromatography operating condition: temperature: 250 DEG C of vaporizer, 60 DEG C of column temperature, detector 250 ℃；Carrier gas is high pure nitrogen；Flow rate of carrier gas is 1.4ml/min；Split ratio is 70: 1；Sample volume is 0.2ml；Test is with reagent The ethyl alcohol or n-butanol of chromatographically pure measure the content of n-butanol using ethyl alcohol, measurement wherein measurement ethanol content uses n-butanol Other alcohol contents use ethyl alcohol or n-butanol.Relative retention time determines that ethyl alcohol is 2.426min and n-butanol 3.151min.The alcohol to be measured of ten kinds of various concentrations of accurate formulation reagent alcohol solution as standard specimen, under GC conditions, The correction factor that each component is calculated with area normalization method, makes the relational graph of determining alcohol index and actual concentrations.It accurately weighs 1.00g carrier is added under 10ml alcohol reagent room temperature and filters after stirring and dissolving 20min, takes filtrate stand-by.In GC conditions Under, needle takes quantitative filtrate to be added to auto-programming sample introduction in autosampler and measures, total divided by normalization with alcohol peak area to be measured Areal calculation goes out filtrate determining alcohol index, substitutes into relational graph and obtains practical determining alcohol, and carrier is finally obtained after conversion In alcohol content.

Embodiment 1

Weigh 2.5g magnesium compound anhydrous magnesium chloride (MgCl₂), a certain amount of butanol and tetrahydrofuran is added, and (boiling point is 65.4 DEG C), after being heated to 60 DEG C of dissolutions, a certain amount of Nonmetallocene ligand is added, continuation is completely dissolved in 60 DEG C of stirrings, is stirred After 2h, precipitating reagent hexane is added and is allowed to precipitate, filters, washs 2 times, each precipitating reagent dosage is identical as additional amount before, is obtained The sediment obtained is at 50 DEG C of temperature (being lower than 15.4 DEG C of solvent boiling point), the dry 8h under the vacuum of absolute pressure 10mBar, Then at 75 DEG C of temperature (being above the boiling point 9.6 DEG C), the dry 4h under the vacuum of absolute pressure 10mBar obtains modification and carries Body, wherein alcohol content is 4.3wt%.

25ml hexane solvent is measured, is added in the modification carrier, was added dropwise to tetrachloro with 15 minutes under agitation Change titanium (TiCl₄) chemical treatments, after reacting 4h at 30 DEG C, filtering, hexane is washed 3 times, and each 25ml is finally vacuumized dry It is dry to obtain load type non-metallocene catalyst.

Nonmetallocene ligand use structural formula forCompound.

Proportion are as follows: the molar ratio of magnesium compound and butanol is 1: 0.5；Magnesium compound is matched with dissolution magnesium compound hexane solvent Than being 1mol: 200ml；Magnesium compound and Nonmetallocene ligand molar ratio are 1: 0.004；Precipitating reagent hexane and dissolution magnesium compound It is 1: 1 with the ratio between the tetrahydrofuran solvent volume of Nonmetallocene ligand；Magnesium compound and chemical treatments titanium tetrachloride molar ratio It is 1: 0.20.

The catalyst is denoted as CAT-1.

Embodiment 2

It is substantially the same manner as Example 1, but be with the following changes:

By the magnesium compound solution than 25.4 DEG C of low boiling point of the solvent at a temperature of in absolute pressure 10mBar Vacuum under dry 10h, then high 14.6 DEG C of the boiling point than the solvent at a temperature of, in the vacuum of absolute pressure 10mBar Lower dry 6h obtains modification carrier, and wherein alcohol content is 3.7wt%.

The catalyst is denoted as CAT-2.

Embodiment 3

Before using chemical treatments processing modification carrier, with selected from triethyl aluminum (Al (C₂H₅)₃) help chemical place Manage agent pretreatment modification carrier.

25ml hexane solvent is measured, is added in the obtained modification carrier of embodiment 1, under agitation first It is added dropwise in 15min and helps chemical treatments triethyl aluminum (Al (C₂H₅)₃), after being stirred to react 1h, filtering, hexane washing 2 times, often Secondary 25ml vacuum drying obtains pretreated modification carrier.

Wherein, magnesium compound with help chemical treatments molar ratio be 1: 0.35.

The catalyst is denoted as CAT-3.

Embodiment 4

It is substantially the same manner as Example 3, but be with the following changes:

Chemical treatments are helped to be changed to methylaluminoxane (MAO).

Wherein: magnesium compound is 1: 0.5 with the molar ratio for helping chemical treatments.

The catalyst is denoted as CAT-4.

Comparative example A

Magnesium compound solution addition precipitating reagent hexane is allowed to precipitate, filters, washs 2 times, each precipitating reagent dosage is therewith Preceding additional amount is identical, and sediment obtained was uniformly heated under the conditions of 100 DEG C (being higher than 34.6 DEG C of solvent boiling point), absolute Dry under the vacuum of pressure 10mBar to obtain modification carrier for 24 hours, wherein alcohol content is 0.04%.

Catalyst is denoted as CAT-A.

Comparative example B

Sediment obtained 30 DEG C (be lower than 35.4 DEG C of solvent boiling point) at a temperature of, in the true of absolute pressure 10mBar The lower dry 1h of sky, obtains modification carrier, wherein alcohol content is 7.6wt%.

Catalyst is denoted as CAT-B.

Embodiment 5 (Application Example)

Load type non-metallocene catalyst CAT-1~4 and CAT-A~B are weighed respectively, with co-catalyst (aluminium methyl Oxygen alkane or triethyl aluminum) it carries out the homopolymerization of ethylene in accordance with the following methods under the following conditions respectively, be copolymerized and prepare supra polymer Weight northylen.

Homopolymerization are as follows: 5L polymerization autoclave, slurry polymerization processes, 2.5L hexane solvent polymerize stagnation pressure 0.8MPa, polymerization temperature 85 DEG C, hydrogen partial pressure 0.2MPa, reaction time 2h.2.5L hexane is added in polymerization autoclave first, opens stirring, then 20mg load type non-metallocene catalyst and catalyst mixture is added, adds hydrogen to 0.2MPa, is finally continually fed into Ethylene keeps polymerization stagnation pressure constant in 0.8MPa.After reaction, gas reactor is vented, releases kettle interpolymer, claims after dry Measure quality.The results are shown in Table 1 for the concrete condition and polymerization evaluation of the polymerization reaction.

Copolymerization are as follows: 5L polymerization autoclave, slurry polymerization processes, 2.5L hexane solvent polymerize stagnation pressure 0.8MPa, polymerization temperature 85 DEG C, hydrogen partial pressure 0.2MPa, reaction time 2h.2.5L hexane is added in polymerization autoclave first, opens stirring, so 20mg load type non-metallocene catalyst and catalyst mixture are added afterwards, is added at one time -1 comonomer 50g of hexene, then Hydrogen is added to 0.2MPa, being finally continually fed into ethylene keeps polymerization stagnation pressure constant in 0.8MPa.After reaction, by gas reactor Emptying releases kettle interpolymer, weighs quality after dry.Concrete condition and polymerization evaluation the result such as table 1 of the polymerization reaction It is shown.

Prepare ultra-high molecular weight polyethylene polymerization are as follows: 5L polymerization autoclave, slurry polymerization processes, 2.5L hexane solvent gather Close stagnation pressure 0.5MPa, 70 DEG C of polymerization temperature, reaction time 6h.2.5L hexane is added in polymerization autoclave first, unlatching is stirred It mixes, 20mg load type non-metallocene catalyst and catalyst mixture, co-catalyst and catalyst activity metal is then added Molar ratio is 100, and being finally continually fed into ethylene keeps polymerization stagnation pressure constant in 0.5MPa.After reaction, gas reactor is vented, Kettle interpolymer is released, weighs quality after dry.The results are shown in Table 2 for the concrete condition and polymerization evaluation of the polymerization reaction.

1. load type non-metallocene catalyst of table is used for olefin polymerization effect list

2. load type non-metallocene catalyst of table is used to prepare ultra-high molecular weight polyethylene polymerization reaction effect list

It is found that the copolymerization effect of catalyst is significant, i.e. catalyst is total to the Contrast on effect as acquired by serial number 1 and 3 in table 1 Poly- activity is higher than homopolymerization activity, and copolyreaction can be improved the heap density of polymer, that is, improve the particle shape of polymer.

The Contrast on effect as acquired by serial number 1 and 2 in table 1 is it is found that co-catalyst needed for polymerization process and catalyst are living Property metal molar it is more suitable than obtained polymerization under the conditions of 50 and 100, thus illustrate that catalyst provided by the present invention is used Required co-catalysis dosage is less when olefinic polymerization.

By the comparison of serial number 1,2 and 3,4 in serial number 1,2 and 7,8 in table 1 and table 2 it is found that by catalyst preparation of the present invention In the process in controlled modification carrier alcohol the obtained catalyst of content, catalytic activity, polymer stacks density and superelevation point The performances such as sub- weight northylen viscosity average molecular weigh are superior to modification carrier and are completely dried or the higher obtained catalyst performance of alcohol content Energy.

Although a specific embodiment of the invention is described in detail above in conjunction with the embodiments, need to refer to Out, the scope of protection of the present invention is not limited by these specific embodiments, but by claims of annex Lai It determines.Those skilled in the art can carry out these embodiments in the range of not departing from technical idea and purport of the invention Change appropriate, and the embodiment after these changes is obviously also included within protection scope of the present invention.

Claims

1. a kind of preparation method of load type non-metallocene catalyst, comprising the following steps:

The step of being dissolved in magnesium compound and Nonmetallocene ligand in solvent in the presence of an alcohol, obtaining magnesium compound solution；

The magnesium compound solution is dry, or precipitating reagent is added into the magnesium compound solution, obtain modification carrier Step, wherein the content of alcohol described in the modification carrier is 3.0-5.0wt%, preferably 3.5-4.5wt%；With

The modification carrier is handled with the chemical treatments selected from Group IVB metallic compound, obtains the load type non-metallocene The step of catalyst.

2. preparation method described in accordance with the claim 1 further includes handling the modification carrier using the chemical treatments Before, with selected from aikyiaiurnirsoxan beta, alkyl aluminum or any combination thereof help chemical treatments pre-process the modification carrier the step of.

3. preparation method described in accordance with the claim 1, which is characterized in that the magnesium compound is selected from magnesium halide, alkoxy halogen Change one of magnesium, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium or a variety of, is preferably selected from magnesium halide One or more, more preferable magnesium chloride.

4. preparation method described in accordance with the claim 1, which is characterized in that the solvent is selected from C_6-12Aromatic hydrocarbon, halogenated C_6-12Virtue One of fragrant hydrocarbon, ester and ether are a variety of, are preferably selected from C_6-12One of aromatic hydrocarbon and tetrahydrofuran are a variety of, and most preferably four Hydrogen furans, and the alcohol is selected from one of fatty alcohol, aromatic alcohol and alicyclic ring alcohol or a variety of, wherein the alcohol is optionally selected from halogen Atom or C_1-6The substituent group of alkoxy replaces, and the alcohol is preferably selected from one of fatty alcohol or a variety of, is more preferably selected from ethyl alcohol With one of butanol or a variety of.

5. preparation method described in accordance with the claim 1, which is characterized in that the Nonmetallocene ligand, which is selected from, has following chemistry One of compound of structural formula is a variety of:

It is preferably selected from one of compound (A) and compound (B) with following chemical structural formula or a variety of:

The compound (A-1) with following chemical structural formula is more preferably selected to compound (A-4) and compound (B-1) to chemical combination One of object (B-4) is a variety of:

In above all of chemical structural formula,

Q is 0 or 1；

D is 0 or 1；

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

F is selected from nitrogen-atoms, nitrogen-containing group, oxygen-containing group, sulfur-containing group, contains seleno group or phosphorus-containing groups, wherein N, O, S, Se and P Respectively atom is used in coordination；

Y is selected from nitrogen-containing group, oxygen-containing group, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se and P are respectively Atom is used in coordination；

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

→ represent singly-bound or double bond；

Represent covalent bond or ionic bond；

R¹To R⁴、R⁶To R²¹It is each independently selected from hydrogen, C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl or safing function group, R²² To R³⁶、R³⁸And R³⁹It is each independently selected from hydrogen, C₁-C₃₀Alkyl or substituted C₁-C₃₀Alkyl, above-mentioned group to each other can phases With can also be different, wherein adjacent group can combine togather bonding or cyclization, be preferably formed as aromatic ring；

The safing function group be selected from halogen, oxygen-containing group, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, Containing tin group, C₁-C₁₀Ester group and nitro；

R⁵Lone pair electrons, hydrogen, C on nitrogen₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl, oxygen-containing group, sulfur-containing group, nitrogenous base Group contains seleno group or phosphorus-containing groups；Work as R⁵For oxygen-containing group, sulfur-containing group, nitrogen-containing group, containing seleno group or when phosphorus-containing groups, R⁵ In N, O, S, P and Se can be used as coordination atom；

The substituted C₁-C₃₀Alkyl is selected from one or more halogens or C₁-C₃₀C of the alkyl as substituent group₁-C₃₀Hydrocarbon Base,

The Nonmetallocene ligand is further preferably selected from one of compound with following chemical structural formula or a variety of:

The Nonmetallocene ligand is most preferably selected from one of compound with following chemical structural formula or a variety of:

6. preparation method according to claim 5, which is characterized in that

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

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

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

The oxygen-containing group is selected from hydroxyl ,-OR³⁴With-T-OR³⁴；

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

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

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

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

The C₁-C₃₀Alkyl is selected from C₁-C₃₀Alkyl, C₇-C₃₀Alkaryl, C₇-C₃₀Aralkyl, C₃-C₃₀Cyclic alkyl, C₂-C₃₀Alkene Base, C₂-C₃₀Alkynyl, C₆-C₃₀Aryl, C₈-C₃₀Condensed ring radical or C₄-C₃₀Heterocycle, wherein the heterocycle contains 1-3 selected from nitrogen The hetero atom of atom, oxygen atom or sulphur atom；

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

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

It is described to be selected from-SnR containing tin group⁵⁰R⁵¹R⁵²、-T-SnR⁵³Or-T-Sn (O) R⁵⁴；

The R⁴²To R⁵⁴It is each independently selected from hydrogen, aforementioned C₁-C₃₀Alkyl or aforementioned substituted C₁-C₃₀Alkyl, above-mentioned group that It can be the same or different around here, wherein adjacent group can combine togather bonding or cyclization, and

The group T is as previously defined.

7. preparation method described in accordance with the claim 1, which is characterized in that the magnesium compound in terms of Mg element with it is described non- The molar ratio of metallocene ligand is 1: 0.0001-1, preferably 1: 0.0002-0.4, more preferable 1: 0.0008-0.2, further preferably 1: 0.001-0.1, the ratio of the magnesium compound and the solvent is 1mol: 75~400ml, preferably 1mol: 150~300ml, More preferable 1mol: 200~250ml, the molar ratio of the magnesium compound and the alcohol in terms of Mg element are 1: 0.02~4.00, It is preferred that 1: 0.05~3.00, more preferable 1: 0.10~2.50, the volume ratio of the precipitating reagent and the solvent is 1: 0.2~5, excellent Select 1: 0.5~2, more preferable 1: 0.8~1.5, and the magnesium compound in terms of Mg element with Group IVB elemental metal The molar ratio of the chemical treatments is 1: 0.01-1, preferably 1: 0.01-0.50, more preferable 1: 0.10-0.30.

8. preparation method described in accordance with the claim 1, which is characterized in that the precipitating reagent is selected from alkane, cycloalkane, alkyl halide One of hydrocarbon and halogenated cycloalkane are a variety of, are preferably selected from pentane, hexane, heptane, octane, nonane, decane, hexamethylene, ring Pentane, cycloheptane, cyclodecane, cyclononane, methylene chloride, dichloro hexane, two chloroheptanes, chloroform, trichloroethanes, three neoprenes Alkane, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane, three bromobutane, chlorocyclopentane, chloro hexamethylene Alkane, chloro cycloheptane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo cycloheptyl One of alkane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane are a variety of, are further preferably selected from hexane, heptane, the last of the ten Heavenly stems One of alkane and hexamethylene are a variety of, most preferably hexane.

9. preparation method described in accordance with the claim 1, which is characterized in that the Group IVB metallic compound is selected from Group IVB metal Halide, Group IVB metal alkyl compound, Group IVB metal alkoxide, Group IVB metal alkyl halides and Group IVB gold Belong to one of alkoxy halide or a variety of, is preferably selected from one of Group IVB metal halide or a variety of, is more preferably selected from TiCl₄、TiBr₄、ZrCl₄、ZrBr₄、HfCl₄And HfBr₄One of or it is a variety of, be most preferably selected from TiCl₄And ZrCl₄In one Kind is a variety of.

10. preparation method according to claim 2, which is characterized in that the aikyiaiurnirsoxan beta is selected from methylaluminoxane, aluminium ethide One of oxygen alkane, isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta are a variety of, are more preferably selected from methylaluminoxane and aluminium isobutyl One of oxygen alkane is a variety of, and the alkyl aluminum is being selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three just In butyl aluminium, triisopentyl aluminium, three n-pentyl aluminium, three hexyl aluminium, three isohesyl aluminium, diethylmethyl aluminium and dimethyl ethyl aluminium It is one or more, be preferably selected from one of trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium or a variety of, most It is preferably selected from one of triethyl aluminum and triisobutyl aluminium or a variety of.

11. preparation method according to claim 2, which is characterized in that the magnesium compound in terms of Mg element with Al The molar ratio for helping chemical treatments of element meter is 1: 0-1.0, preferably 1: 0-0.5, more preferable 1: 0.1-0.5.

12. preparation method described in accordance with the claim 1, which is characterized in that the acquisition modifies the step of carrier according to following Mode carries out:

By the magnesium compound solution 5-50 DEG C lower than the solvent boiling point at a temperature of, it is 10-30 DEG C preferably low, in absolute pressure Under the vacuum of power 2-100mBar, preferably 5-50mBar, dry 2-30h, preferably 4-12h, then from the solvent boiling point to than At a temperature of high 30 DEG C of the solvent boiling point, preferably from the solvent boiling point at a temperature of 20 DEG C higher than the solvent boiling point, Under the vacuum of absolute pressure 2-100mBar, preferably 5-50mBar, dry 1-20h, preferably 2-8h obtain the modification carrier,

Alternatively, precipitating reagent is added into the magnesium compound solution, by sediment obtained (optionally after wash) than It is 10-30 DEG C preferably low at a temperature of the solvent boiling point is 5-50 DEG C low, under the vacuum of absolute pressure 2-100mBar, preferably 5- 50mBar, dry 2-30h, preferably 4-12h, then from the solvent boiling point to 30 DEG C of temperature higher than the solvent boiling point Under, preferably from the solvent boiling point at a temperature of 20 DEG C higher than the solvent boiling point, in the vacuum of absolute pressure 2-100mBar Under, preferably 5-50mBar, dry 1-20h, preferably 2-8h obtain the modification carrier.

13. a kind of load type non-metallocene catalyst, it is by according to the described in any item preparation method systems of claim 1-12 It makes.

14. a kind of olefine polymerizing process, which is characterized in that including being urged with load type non-metallocene according to claim 13 Agent is major catalyst, with one in aikyiaiurnirsoxan beta, alkyl aluminum, halogenated alkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt Kind or a variety of the step of being co-catalyst, making alkene homopolymerization or copolymerization.