CN109485761A

CN109485761A - Load type non-metallocene catalyst, preparation method and its application

Info

Publication number: CN109485761A
Application number: CN201710814594.3A
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 in solvent in the presence of an alcohol, obtain magnesium compound solution；Make the step of optionally mixing with the magnesium compound solution by the porous carrier that thermal activation treatment and/or chemical activation are handled, obtain mixed serum；The mixed serum is dry, or the step of precipitating reagent is added, obtains complex carrier into the mixed serum, wherein the content of alcohol described in the complex carrier is 0.5-2.5wt%；The step of handling the complex carrier with the chemical treatments selected from Group IVB metallic compound, obtaining modification complex carrier；The step of handling the modification complex carrier with Nonmetallocene ligand or Nonmetallocene complex, 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 CN 1539855A, CN 1539856A, CN 1789291A, CN 1789292A, CN 1789290A, WO/2006/063501,200510119401.x etc. use various modes and are loaded, and it is non-to obtain support type Metallocene catalyst, but these patents all refer to by the Nonmetallocene organic compound containing transition metal (or for it is non-cyclopentadienyl gold Metal catalyst or Nonmetallocene complex) on the carrier that is carried on that treated or non-metallocene catalyst load capacity compared with It is low or it is not bery close in conjunction with carrier.

Existing olefin polymerization catalysis patent is mostly based on metallocene catalyst, as US 4808561, US 5240894, CN 1049439、CN 1136239、CN 1344749、CN 1126480、CN 1053673、CN 1307594、CN 1130932、 CN 1103069, CN 1363537, CN 1060179, US574417, EP685494, US4871705 and EP0206794 etc., But 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.

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 the electron donor, it is obtained after processing.

Patent CN200610026766.2 is similar therewith, discloses a kind of containing heteroatomic organic compound and its neat Application in Ge Le-Natta catalyst.

A kind of magnesium compound load type non-metallocene catalyst and its preparation side disclosed in patent CN200710162676.0 Method is directly to be contacted Nonmetallocene ligand with the magnesium compound containing catalytically-active metals by supported method in situ It obtains.But contact of the catalytically-active metals described in it with magnesium compound, which refers to for Group IVB metallic compound to be added to, to be had become In the magnesium compound solid of type (such as magnesium compound solid or magnesium compound solid of modification), such contact cannot be accomplished to urge Change sufficiently reacting for active metal and magnesium compound, the obtained magnesium compound carrier containing catalytically-active metals necessarily out-phase , be not it is intermolecular come into full contact with and react, thus limit subsequent addition Nonmetallocene ligand effect completely play.

Equally, patent CN200710162667.1 discloses a kind of magnesium compound load type non-metallocene catalyst and its system Preparation Method also has similar problem.It is by supported method in situ by the compound of catalytically-active metals with contain it is non- Obtained from the magnesium compound of metallocene ligand directly contacts.But the contact described in it refers to, and Nonmetallocene ligand solution is added Into molded magnesium compound solid (such as magnesium compound solid or magnesium compound solid of modification), such contact cannot Accomplish sufficiently reacting for Nonmetallocene ligand and magnesium compound, the magnesium compound carrier of the obtained ligand containing Nonmetallocene is necessarily Out-phase, be not it is intermolecular come into full contact with and react, thus limit Nonmetallocene ligand effect complete performance.

The above problem is still remained based on the applied PCT Patent PCT/CN2008/001739 of two above patent.

Higher catalytic activity is shown in olefin polymerization process by the catalyst of carrier of anhydrous magnesium chloride, but such Catalyst is highly brittle, is easily broken in polymer reactor, bad so as to cause polymer morphology.Silicon dioxide carried catalysis Agent has good mobility, can be used for gas fluidised bed polymerisation, but silicon dioxide carried metallocene and non-metallocene catalyst Then show lower catalytic activity.So if magnesium chloride and silica are organically combined well, it is possible to make Standby to have provided high catalytic activity, granule size is controllable and the catalyst of good abrasion strength resistance.

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 Group IVB transition metal halide, then directly reacts with ligand anion, to realize in a step The synthesis and load of metallocene catalyst.But it is 1: 1 that this method, which requires the molar ratio of transition metal and ligand, and needs to be added Any proton, such as butyl lithium, and used ligand is the cyclopentadienyl gold 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-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, Ni (acac) the 2/TiCl4 composite catalyst modified with alpha-diimine ligand L.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.

Patent CN200910210991.5 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 mixing the porous carrier optionally Jing Guo thermal activation treatment with the magnesium compound solution, obtaining mixed serum；To institute The step of stating and precipitating reagent be added in mixed serum, obtaining complex carrier；With the chemical treatments to be selected from Group IVB metallic compound The step of handling the complex carrier, obtaining the load type non-metallocene catalyst.According to the alcohol of the visible introducing of disclosure It acts on the cosolvent only as magnesium compound and Nonmetallocene ligand, and then dries and removes in drying process.

As seen from the above, load type non-metallocene catalyst common problem existing in the prior art is to be catalyzed The out-phase composition formed in the preparation process of agent and distribution, limit polymerization catalyst product property and its particle shape.

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 complex 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:

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

Keep the porous carrier and the magnesium compound solution that optionally handle by thermal activation treatment and/or chemical activation mixed The step of closing, obtaining mixed serum；

The mixed serum is dry, or the step of precipitating reagent is added, obtains complex carrier into the mixed serum, Wherein the content of alcohol described in the complex carrier is 0.5-2.5wt%, preferably 1.0-2.0wt%；

The complex carrier is handled with the chemical treatments selected from Group IVB metallic compound, obtains modification complex carrier Step；With

The modification complex carrier is handled with Nonmetallocene ligand or Nonmetallocene complex, it is non-to obtain the support type The step of metallocene 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 preparation method simple process of load type non-metallocene catalyst of the invention is feasible, and Nonmetallocene ligand is equably It is distributed in magnesium compound, 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 strictly being controlled in complex carrier drying process 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.

According to the present invention, it is related to a kind of preparation method of load type non-metallocene catalyst, comprising the following steps: make magnesium Close the step of object is dissolved in solvent in the presence of an alcohol, obtains magnesium compound solution；Make optionally to pass through thermal activation treatment and/or The step of porous carrier of chemical activation processing mixes with the magnesium compound solution, obtains mixed serum；By the mixing slurry Liquid is dry, or the step of precipitating reagent is added, obtains complex carrier into the mixed serum, wherein institute in the complex carrier The content for stating alcohol is 0.5-2.5wt%；The complex carrier is handled with the chemical treatments selected from Group IVB metallic compound, is obtained The step of complex carrier must be modified；The modification complex carrier is handled with Nonmetallocene ligand or Nonmetallocene complex, The step of 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, magnesium compound is made to be dissolved in solvent appropriate in the presence of an alcohol (i.e. for dissolving the magnesium Close the solvent of object) 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 can be added to by the solvent and the alcohol shape At in the mixed solvent dissolved, or the magnesium compound is added in the solvent, and subsequently or simultaneously add alcohol It 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.

The preparation time (dissolution time of the i.e. described magnesium compound) of the magnesium compound solution is not limited particularly It is fixed, but generally 0.5~for 24 hours, preferably 4~for 24 hours.In the preparation process, stirring can use to promote the magnesium compound Dissolution.Any form, such as agitating paddle (revolving speed is generally 10~1000rpm) etc. can be used in the stirring.As needed, have When can promote to dissolve by heating appropriate.

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.

By mixing the porous carrier with the magnesium compound solution, thus to obtain mixed serum.

According to the present invention, the mixed process of the porous carrier and the magnesium compound solution can use usual way It carries out, there is no particular limitation.For example can enumerate, under room temperature to the preparation temperature of the magnesium compound solution, Xiang Suoshu The metered porous carrier in magnesium compound solution, or the metered magnesium compound is molten into the porous carrier Liquid mixes 0.1~8h, preferably 0.5~4h, optimal 1~2h (when necessary by stirring).

According to the present invention, the dosage as the porous carrier, so that the magnesium compound is (with the magnesium compound solution In the magnesium compound solid meter that contains) with the mass ratio of the porous carrier reach 1: 0.1-20, preferably 1: 0.5-10, more preferably 1∶1-5。

According to the present invention, the mixed serum is a kind of half dry system, and there is no free liquid.Although not necessarily, But in order to ensure the uniformity of system, the mixed serum preferably carried out after preparation certain time (2~48h, preferably 4~for 24 hours, Most preferably 6~18h) closed standing.

The porous carrier is specifically described below.

According to the present invention, as the porous carrier, for example this field can be enumerated and urged in manufacture load type olefin polymerization When agent as carrier those conventional use of organic or inorganic porosu solids.

Specifically, as the Porous-Organic solid, for example olefin homo or copolymer, polyvinyl alcohol can be enumerated Or its copolymer, cyclodextrin, (total) polyester, (total) polyamide, ryuron or copolymer, Voncoat R 3310 or total Polymers, methacrylate homopolymer or copolymer, styrene homopolymers or copolymer etc. and these homopolymers or copolymer Partial cross-linked form, wherein it is preferred that the styrene polymerization of partial cross-linked (for example the degree of cross linking is at least 2% but less than 100%) Object.

A preferred embodiment according to the present invention has preferably on the surface of the Porous-Organic solid and such as selects It is mono-substituted from hydroxyl, primary amino group, secondary amino group, sulfonic group, carboxyl, amide groups, the mono-substituted amide groups of N-, sulfoamido, N- The active function groups of any one or more in sulfoamido, sulfydryl, acylimino and hydrazide group, wherein it is preferred that carboxyl and hydroxyl At least one of base.

According to an embodiment of the invention, using it is preceding to the Porous-Organic solid carry out thermal activation treatment and/or Chemical activation processing.

According to the present invention, the Porous-Organic solid can only carry out thermal activation treatment before use, or before use Chemical activation processing can also be only carried out, or can successively carry out the thermal activation according to arbitrary built-up sequence using preceding Processing and chemical activation processing, are not particularly limited.

The thermal activation treatment can carry out in usual way.Such as to described at reduced pressure conditions or under inert atmosphere Porous-Organic solid is heated.Inert atmosphere mentioned here, which refers to, only to be contained extremely micro or not to contain in gas It can be with the component of the Porous-Organic solid reaction.As the inert atmosphere, for example nitrogen or rare gas gas can be enumerated Atmosphere, preferably nitrogen atmosphere.Due to the poor heat resistance of Porous-Organic solid, the thermal activation process is described organic more not destroy The structure of hole solid itself and it basic composition is premise.Generally, the temperature of the thermal activation be 50~400 DEG C, preferably 100~ 250 DEG C, and the thermal activation time be 1~for 24 hours, preferably 2~12h.

After thermal activation/chemical activation processing, positive pressure saves backup the Porous-Organic solid needs under an inert atmosphere.

As the inorganic porous solids, for example the periodic table of elements IIA, IIIA, IVA or Group IVB metal can be enumerated Refractory oxides (such as silica (also known as silica or silica gel), aluminium oxide, magnesia, titanium oxide, zirconium oxide or oxidation Thorium etc.) or these metals any infusibility composite oxides (such as oxidation sial, oxidation magnalium, titanium oxide silicon, titanium oxide Magnesium and titanium oxide aluminium etc.) and clay, molecular sieve (such as ZSM-5 and MCM-41), mica, montmorillonite, bentonite and diatomite Deng.As the inorganic porous solids, it can also enumerate and pyrohydrolysis is passed through by gaseous metal halide or gaseous silicon compound And the oxide generated, such as the silica gel obtained by silicon tetrachloride pyrohydrolysis, or obtained by alchlor pyrohydrolysis Aluminium oxide etc..

As the inorganic porous solids, preferably silica, aluminium oxide, magnesia, oxidation sial, oxidation magnalium, oxygen Change titanium silicon, titanium dioxide, molecular sieve and montmorillonite etc., particularly preferred silica.

According to the present invention, suitable silica can manufacture by conventional method, or can be arbitrary commercially available Commercial product, for example the Grace 955, Grace 948, Grace SP9-351, Grace of Grace company can be enumerated SP9-485, Grace SP9-10046, Davsion Syloid 245 and ES70, ES70X of Aerosil812, Ineos company, ES70Y, ES70W, ES757, EP10X and EP11 and the CS-2133 and MS-3040 of Pq Corp..

A preferred embodiment according to the present invention, with hydroxyl etc. preferably on the surface of the inorganic porous solids Active function groups.

According to the present invention, in one embodiment, thermal activation treatment is being carried out to the inorganic porous solids using preceding And/or chemical activation processing.

According to the present invention, the inorganic porous solids can only carry out thermal activation treatment before use, or before use Chemical activation processing can also be only carried out, or can successively carry out the thermal activation according to arbitrary built-up sequence using preceding Processing and chemical activation processing, are not particularly limited.

The thermal activation treatment can carry out in usual way, such as to described at reduced pressure conditions or under inert atmosphere Inorganic porous solids are heated.Inert atmosphere mentioned here, which refers to, only to be contained extremely micro or not to contain in gas The component that can be reacted with the inorganic porous solids.As the inert atmosphere, for example nitrogen or rare gas gas can be enumerated Atmosphere, preferably nitrogen atmosphere.Generally, the temperature of the thermal activation be 200-800 DEG C, preferably 400~700 DEG C, most preferably 400~ 650 DEG C, heating time is such as 0.5~for 24 hours, preferably 2~12h, most preferably 4~8h.

After thermal activation/chemical activation processing, positive pressure saves backup the inorganic porous solids needs under an inert atmosphere.

According to the present invention, at the chemical activation that the Porous-Organic solid or the inorganic porous solids carry out Reason can carry out in usual way.For example, can enumerate using chemical activating agent come to the Porous-Organic solid or institute State the method that inorganic porous solids carry out chemical activation processing.

The chemical activating agent is specifically described first below.

According to the present invention, using Group IVB metallic compound as the chemical activating agent.

As the Group IVB metallic compound, for example can enumerate selected from Group IVB metal halide, Group IVB metal alkyl Compound, Group IVB metal alkoxide, Group IVB metal alkyl halides and Group IVB metal alkoxide halide are at least It is a kind of.

As the Group IVB metal halide, the Group IVB metal alkyl compound, the Group IVB metal alkoxide Object, the Group IVB metal alkyl halides and the Group IVB metal alkoxide halide are closed, for example following general formula can be enumerated The compound of structure:

M(OR¹)_mX_nR² _4-m-n

Wherein:

M is 0,1,2,3 or 4；

N is 0,1,2,3 or 4；

M is Group IVB metal, 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 the Group IVB metal halide, for example titanium tetrafluoride (TiF can be enumerated₄), titanium tetrachloride (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 the Group IVB 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 the Group IVB 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 Base oxethyl titanium (Ti (OCH₃)₃(OCH₃CH₂)), three isobutoxy methoxyl group titanium (Ti (OCH₃)(i-OC₄H₉)₃), two isobutoxies Dimethoxy titanium (Ti (OCH₃)₂(i-OC₄H₉)₂), trimethoxy isobutoxy titanium (Ti (OCH₃)₃(i-OC₄H₉)), three isobutyl oxygen Base oxethyl titanium (Ti (OCH₃CH₂)(i-OC₄H₉)₃), two isobutoxy diethoxy titanium (Ti (OCH₃CH₂)₂(i-OC₄H₉)₂), three Ethyoxyl isobutoxy titanium (Ti (OCH₃CH₂)₃(i-OC₄H₉)), three n-butoxy methoxyl group titanium (Ti (OCH₃)(OC₄H₉)₃), two N-butoxy dimethoxy titanium (Ti (OCH₃)₂(OC₄H₉)₂), trimethoxy titanium n-butoxide (Ti (OCH₃)₃(OC₄H₉)), three just Butoxymethoxy titanium (Ti (OCH₃CH₂)(OC₄H₉)₃), two n-butoxy diethoxy titanium (Ti (OCH₃CH₂)₂(OC₄H₉)₂), three Ethyoxyl 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 the Group IVB metal alkyl halides, for example trimethyl ammonia chloride titanium (TiCl (CH can be enumerated₃)₃), three second Base titanium chloride (TiCl (CH₃CH₂)₃), triisobutyl titanium chloride (TiCl (i-C₄H₉)₃), three n-butylmagnesium chloride titanium (TiCl (C₄H₉)₃), dimethyl titanium chloride (TiCl₂(CH₃)₂), diethyl titanium chloride (TiCl₂(CH₃CH₂)₂), diisobutyl dichloro Change titanium (TiCl₂(i-C₄H₉)₂), three n-butylmagnesium chloride titanium (TiCl (C₄H₉)₃), methyl titanium trichloride (Ti (CH₃)Cl₃), ethyl three Titanium chloride (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 the Group IVB metal alkoxide halide, for example trimethoxy titanium chloride (TiCl (OCH can be enumerated₃)₃)、 Triethoxy titanium chloride (TiCl (OCH₃CH₂)₃), three isobutoxy titanium chloride (TiCl (i-OC₄H₉)₃), three n-butoxy chlorinations Titanium (TiCl (OC₄H₉)₃), dimethoxy titanium chloride (TiCl₂(OCH₃)₂), diethoxy titanium chloride (TiCl₂ (OCH₃CH₂)₂), two isobutoxy titanium chloride (TiCl₂(i-OC₄H₉)₂), three n-Butoxyl titanium-chlorides (TiCl (OC₄H₉)₃)、 Methoxytitanium trichloride (Ti (OCH₃)Cl₃), ethyoxyl 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 isobutoxies Bromination 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 the Group IVB metallic compound, the preferably described Group IVB metal halide, more preferable TiCl₄、TiBr₄、 ZrCl₄、ZrBr₄、HfCl₄And HfBr₄, most preferably TiCl₄And ZrCl₄。

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

It, can be by there is the chemical activating agent to be utilized to activate when the chemical activating agent is at normal temperature liquid The mode that the chemical activating agent of predetermined amount is directly added dropwise in Porous-Organic solid or inorganic porous solids uses the chemistry Activator.

When the chemical activating agent is 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 activating agent.It certainly, can also sometimes according to needs when the chemical activating agent is at normal temperature liquid To use the chemical activating agent as a solution, it is not particularly limited.

When preparing the solution of the chemical activating agent, to used solvent at this time, there is no particular limitation, as long as its The chemical activating agent can be dissolved.

Specifically, C can be enumerated_5-12Alkane, C_5-12Cycloalkane, halogenated C_5-12Alkane, halogenated C_5-12Cycloalkane, C_6-12Virtue Hydrocarbon or halogenated C_6-12Aromatic hydrocarbons etc., for example pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, ring can be enumerated Pentane, hexamethylene, cycloheptane, cyclooctane, toluene, ethylbenzene, dimethylbenzene, chloro-pentane, chloro-hexane, chloro heptane, chloro are pungent Alkane, chloro nonane, chloro decane, chloro hendecane, chlorinated dodecane, chlorocyclohexane, chlorotoluene, chloro ethylbenzene and chloro Dimethylbenzene etc., wherein it is preferred that pentane, hexane, decane, hexamethylene and toluene, most preferably hexane and toluene.

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

In addition, to concentration of the chemical activating agent in its solution, there is no particular limitation, and it is appropriate to can according to need Selection, as long as it can be realized the chemical activating agent with predetermined amount to implement the chemical activation.As previously mentioned, such as Fruit chemical activating agent is liquid, the activation can be directly carried out using chemical activating agent, but can also be modulated into It is used after chemical activation agent solution.

It is expedient to molar concentration of the chemical activating agent in its solution is usually set to 0.01~1.0mol/L, But it is not limited to this.

It as the method for carrying out the chemical activation, for example can enumerate, be solid-state (such as four chlorinations in chemical activating agent Zirconium) in the case where, the solution of the chemical activating agent is prepared first, then to Porous-Organic solid to be activated or inorganic porous The solution of the chemical activating agent containing predetermined amount is added and (is preferably added dropwise) in solid, to carry out chemical activation reaction. In the case where chemical activating agent is liquid (such as titanium tetrachloride), directly the chemical activating agent of predetermined amount can be added In (preferably be added dropwise) Porous-Organic solid or inorganic porous solids to be activated, to carry out chemical activation reaction, or should Chemical activating agent is prepared into after solution, is added and (is preferably added dropwise) into Porous-Organic solid to be activated or inorganic porous solids The solution of the chemical activating agent containing predetermined amount, to carry out chemical activation reaction.

In general, making the chemical activation reaction (must under the reaction temperature of -30~60 DEG C (preferably -20~30 DEG C) By stirring when wanting) progress 0.5~for 24 hours, preferably 1~8h, more preferable 2~6h.

After chemical activation reaction terminates, by being filtered, washed and dried, it can be obtained by the organic more of chemical activation Hole solid or inorganic porous solids.

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 activating agent.As needed, which generally carries out 1~8 time, preferably 2 ~6 times, most preferably 2~4 times.

The drying can be carried out using conventional method, such as under inert gas seasoning, boulton process or vacuum Heat drying method, preferably inert gas seasoning or heating under vacuum seasoning, most preferably heating under vacuum seasoning.It is described dry Dry temperature range is generally room temperature to 140 DEG C, and drying time is generally 2-20h, and but it is not limited to this.

According to the present invention, to the surface area of the porous carrier, there is no particular limitation, but generally 10~1000m²/g (BET method measurement), preferably 100~600m²/g；The pore volume (determination of nitrogen adsorption) of the porous carrier is generally 0.1~4cm³/ G, preferably 0.2~2cm³/ g, and its average grain diameter (laser particle analyzer measurement) preferably 1~500mm, more preferable 1~100mm.

According to the present invention, the porous carrier can be arbitrary form, for example, micropowder, granular, spherical, aggregation or Other forms.

By precipitating reagent metered into the mixed serum, it is precipitated out solid matter from the mixed serum, Thus to obtain the complex carrier.Alternatively, by by the mixed serum convection drying, thus to obtain the complex carrier.

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 mixed serum, and be conducive to the final precipitating of solid product. 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, compound load can be obtained Body.The method being filtered, washed and dried is not particularly limited, can according to need routinely is made using this field Those of with.

As needed, the washing is general carries out 1-6 times, preferably 2-3 times.Wherein, washer solvent it is preferable to use with it is heavy The identical solvent of shallow lake agent, however, you can also not same.

According to the present invention, by the way that the mixed serum is dry, or by the solid product (optionally after wash) It is dried, the content of alcohol described in the complex carrier is controlled as 0.5-2.5wt%, preferably 1.0-2.0wt%.

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, according to the present invention, the drying mode (including drying temperature, dry vacuum degree and drying time) Meet aforementioned claim of the present invention with alcohol content in the complex carrier to be limited.For example, by the mixed serum than the solvent It is 10-30 DEG C preferably low at a temperature of 5-40 DEG C of low boiling point, under the vacuum of absolute pressure 2-100mBar, preferably 5-50mBar, Dry 2-48h, preferably 4-24h, then from the solvent boiling point to 50 DEG C higher than the solvent boiling point at a temperature of, preferably From the solvent boiling point at a temperature of 40 DEG C higher than the solvent boiling point, under the vacuum of absolute pressure 2-100mBar, preferably 5-50mBar, dry 1-24h, preferably 2-12h, thus to obtain the complex carrier.Alternatively, being added into the mixed serum Precipitating reagent, by sediment obtained (optionally after wash) 5-40 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, preferably 5-50mBar, dry 2-48h, preferably 4-24h, then From the solvent boiling point to 50 DEG C higher than the solvent boiling point at a temperature of, preferably from the solvent boiling point to than the solvent At a temperature of high 40 DEG C of boiling point, under the vacuum of absolute pressure 2-100mBar, preferably 5-50mBar, dry 1-24h, preferably 2- 12h, thus to obtain the complex carrier.

Then, the complex carrier is handled with the chemical treatments selected from Group IVB metallic compound, obtains and modifies compound load The step of body.

The chemical treatments are specifically described below.

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

As the Group IVB metallic compound, for example Group IVB metal halide, IV B race metal alkyl can be enumerated Close object, Group IVB metal alkoxide, Group IVB metal alkyl halides and Group IVB metal alkoxide halide.

As the Group IVB metal halide, the Group IVB metal alkyl compound, IV B race metal alkoxide Compound, the Group IVB metal alkyl halides and the Group IVB metal alkoxide halide, for example can enumerate following logical The compound of formula (IV) structure:

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；

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

As the Group IVB metal alkyl halides, for example trimethyl ammonia chloride titanium (TiCl (CH can be enumerated₃)₃), three second Base titanium chloride (TiCl (CH₃CH₂)₃), triisobutyl titanium chloride (TiCl (i-C₄H₉)₃), three n-butylmagnesium chloride titanium (TiCl (C₄H₉)₃), dimethyl titanium chloride (TiCl₂(CH₃)₂), diethyl titanium chloride (TiCl₂(CH₃CH₂)₂), diisobutyl 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)；

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

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 structure of (such as dissolution) carrier.

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.

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 complex 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 complex carrier of reason, and make chemical treatment reaction (must under the reaction temperature of -30-60 DEG C (preferably -20-30 DEG C) By stirring when wanting) progress 0.5~for 24 hours, then preferably 1~8h, more preferable 2~6h are filtered, wash and dry.

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 Group IVB 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 complex carrier using the chemical treatments, with selected from aikyiaiurnirsoxan beta, alkyl aluminum or any combination thereof Help chemical treatments pre-process the complex 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 complex carrier replace with it is described through pretreatment Complex 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 compound load of chemical treatments is helped described in quasi- (being preferably added dropwise) described help metered in body is chemically treated agent solution (containing chemical treatments are helped described in predetermined amount), or It helps the chemical treatment agent solution amount of falling into a trap that the complex carrier is added to described, reaction mixture is consequently formed, it is made to react 1-8h, It is preferred that 2-6h, most preferably 3-4h (when necessary by stirring).Then, by pretreatment product obtained by filtering, washing (1~6 time, preferably 1~3 time) and optionally drying are washed, and is separated from the reaction mixture, alternatively, can also be without The separation and subsequent reaction step (chemical treatment step i.e. above-mentioned) is directly used in the form of mixed liquor.At this point, due to A certain amount of solvent is contained in the mixed liquor, it is possible to accordingly reduce solvent involved in the subsequent reactions step Dosage.

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。

According to the present invention, the modification complex carrier is handled with Nonmetallocene ligand or Nonmetallocene complex, obtained The step of load type non-metallocene catalyst.

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 Group IVB metallic compound used in (such as the hetero atoms such as N, O, S, Se and P) and the present invention as chemical treatments Group IVB metallic atom occurs complexation reaction and forms coordinate bond, is consequently formed using the Group IVB metallic atom as center metallic atom The complex (Nonmetallocene complex i.e. of the present invention) of 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 is selected 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 seleno Group 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.

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 Group IVB 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 the Group IVB metallic atom occur complexation reaction and form coordinate bond.In general, The inert substituent is 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.

According to the present invention, in order to measure with it is easy to operate, the Nonmetallocene ligand makes as a solution if necessary ?.

When preparing the solution of the Nonmetallocene ligand, to solvent used at this time, there is no particular limitation, as long as can To dissolve the Nonmetallocene ligand and not destroy the existing carrier structure of (such as dissolution) carrier.As described Solvent, for example C can be enumerated_6-12Aromatic hydrocarbon, halogenated C_6-12Aromatic hydrocarbon, halogenated C_1-10Alkane, one of ester and ether or a variety of. It specifically can such as enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromine For ethylbenzene, methylene chloride, dichloroethanes, ethyl acetate and tetrahydrofuran etc..Wherein, preferably C_6-12Aromatic hydrocarbon, tetrahydrofuran and Methylene chloride.

When dissolving the Nonmetallocene ligand, can according to need using stirring (revolving speed of the stirring is generally 10~ 500rpm)。

According to the present invention, the Nonmetallocene ligand is generally 0.02~0.30 gram/milli relative to the ratio of the solvent It rises, preferably 0.05~0.15 grams per milliliter, but is not limited thereto.

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

It include that n group X and m is more with the central metal atom M ligand for forming coordinate bond according to the chemical structural formula Tooth ligand (structural formula in bracket).According to the chemical structural formula of the multidentate ligand, group A, D and E (coordination group) are logical Coordination atom contained by these groups (such as the hetero atoms such as N, O, S, Se and P) is crossed to match with central metal atom M formation Position key.

According to the present invention, the negative electrical charge sum of all ligand (including the group X and the multidentate ligand) institute's bands is exhausted It is identical as the positively charged absolute value of the central metal atom M to being worth.

In one more specifically embodiment, the Nonmetallocene complex is selected from following chemical structural formula Compound (A) and compound (B).

In one more specifically embodiment, the Nonmetallocene complex is selected from following chemical structural formula Compound (A-1) is 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；

M is 1,2 or 3；

M is selected from periodic table of elements III-th family to the central metal atom of X I race metallic atom, preferably group ivb gold Belong to atom, for example Ti (IV), Zr (IV), Hf (IV), Cr (III), Fe (III), Ni (II), Pd (II) or Co can be enumerated (II)；

N is 1,2,3 or 4, the valence state depending on the central metal atom M；

X is selected from halogen, hydrogen atom, C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl, nitrogen-containing group, contains sulfenyl at oxygen-containing group Group, boron-containing group, group containing aluminium base, phosphorus-containing groups, silicon-containing group, germanic group contain tin group, and multiple X can be identical, can also It, can also bonding or cyclization each other with difference；

Y be selected from oxygen atom, 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；

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；

--- represent coordinate bond, 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, and

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 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 Selected from C₁-C₃₀Alkyl or substituted C₁-C₃₀Alkyl.The R³⁷Selected from hydrogen, C₁-C₃₀Alkyl or substituted C₁-C₃₀Alkyl.

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 group R⁵) with not substantive dry of the complexation process of the central metal atom M It disturbs；In other words, it is limited by the chemical structure of multidentate ligand of the present invention, these substituent groups have no ability to or have no chance (for example being influenced by steric hindrance etc.) and the central metal atom M occur complexation reaction and form coordinate bond.In general, institute It states inert substituent and is such as selected from halogen or C₁-C₃₀Alkyl (preferably C₁-C₆Alkyl, such as isobutyl group).

In the context of the present invention, the boron-containing group is selected from BF₄ ^-、(C₆F₅)₄B^-Or (R⁴⁰BAr₃)^-；It is described to contain aluminium Group is selected from alkyl aluminum, AlPh₄ ^-、AlF₄ ^-、AlCl₄ ^-、AlBr₄ ^-、 AlI₄ ^-Or R⁴¹AlAr₃ ^-；The silicon-containing group be selected from- SiR⁴²R⁴³R⁴⁴Or-T-SiR⁴⁵；The germanic group is selected from-GeR⁴⁶R⁴⁷R⁴⁸Or-T-GeR⁴⁹；It is described containing tin group be selected from- SnR⁵⁰R⁵¹R⁵²、 -T-SnR⁵³Or-T-Sn (O) R⁵⁴, wherein Ar represents C₆-C₃₀Aryl.R⁴⁰To R⁵⁴It is each independently selected from hydrogen, preceding The C stated₁-C₃₀Alkyl or substituted C above-mentioned₁-C₃₀Alkyl, above-mentioned group can be the same or different to each other, wherein phase Adjacent group can combine togather bonding or cyclization.Wherein, group T is as defined above.

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

The Nonmetallocene complex is preferably selected from following compound:

The Nonmetallocene complex is further preferably selected from following compound:

The Nonmetallocene complex is more preferably selected from following compound:

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

According to the present invention, the multidentate ligand in the Nonmetallocene complex be not in this field as electronics to The usually used diether compounds of body compound.

The Nonmetallocene complex or the multidentate ligand can be according to any methods well known by persons skilled in the art It is manufactured.About the particular content of its manufacturing method, such as reference can be made to WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 etc., this specification introduce the full text of these documents as reference with regard to this.

According to the present invention, in order to measure with it is easy to operate, the Nonmetallocene complex is if necessary as a solution It uses.

When preparing the solution of the Nonmetallocene complex, to solvent used at this time, there is no particular limitation, as long as The Nonmetallocene complex can be dissolved and do not destroy the existing carrier structure of (such as dissolution) carrier.Make For the solvent, for example C can be enumerated_6-12Aromatic hydrocarbon, halogenated C_6-12Aromatic hydrocarbon, halogenated C_1-10One of alkane, ester and ether or It is a variety of.It specifically can such as enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo first Benzene, bromo ethylbenzene, methylene chloride, dichloroethanes, ethyl acetate and tetrahydrofuran etc..Wherein, preferably C_6-12Aromatic hydrocarbon, dichloromethane Alkane and tetrahydrofuran.

When dissolving the Nonmetallocene complex, can according to need use stirring, (revolving speed of the stirring is generally 10 ~500rpm).

According to the present invention, it is convenient that, the Nonmetallocene complex is generally 0.02 relative to the ratio of the solvent ~0.30 grams per milliliter, preferably 0.05~0.15 grams per milliliter, but is not limited thereto.

As the method for carrying out the processing with the Nonmetallocene ligand or the Nonmetallocene complex, such as can To enumerate, the solution of the Nonmetallocene ligand or the Nonmetallocene complex is prepared first, then at -30-60 DEG C At a temperature of (preferably -20-30 DEG C), (being preferably added dropwise) solution metered into the modification complex carrier of quasi- processing (contains Have the Nonmetallocene ligand of predetermined amount perhaps Nonmetallocene complex) or metered into the solution described repair It adorns complex carrier, carries out processing reaction under the reaction temperature of -30-60 DEG C (preferably -20-30 DEG C) (when necessary by stirring) 0.5~for 24 hours, then preferably 1~8h, more preferable 2~6h are filtered, optionally washing and dry.

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 Nonmetallocene ligand or Nonmetallocene complex.The washing generally carries out 1 ~8 times, preferably 2~6 times, most preferably 2~4 times.

According to the present invention, the molar ratio of the magnesium compound in terms of Mg element and the Nonmetallocene complex is 1: 0.01-1, preferably 1: 0.04-0.4, more preferable 1: 0.08-0.2.

According to the present invention, the molar ratio of the magnesium compound in terms of Mg element and the Nonmetallocene ligand is 1: 0.0001-1, preferably 1: 0.0002-0.4, more preferable 1: 0.0008-0.2, further preferred 1: 0.001-0.1.

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 molar ratio of the magnesium compound in terms of Mg element and the Nonmetallocene complex is 1: 0.01-1, preferably 1: 0.04-0.4, more preferable 1: 0.08-0.2, the magnesium compound and the non-cyclopentadienyl gold in terms of Mg element The molar ratio of metal ligand be 1: 0.0001-1, preferably 1: 0.0002-0.4, more preferable 1: 0.0008-0.2, further preferred 1: The ratio of 0.001-0.1, the magnesium compound and the solvent be 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 magnesium compound in terms of magnesium compound solid with it is described porous The mass ratio of carrier is 1: 0.1-20, preferably 1: 0.5-10, more preferable 1: 1-5, the volume ratio of the precipitating reagent and the solvent Be 1: 0.2~5, preferably 1: 0.5~2, more preferable 1: 0.8~1.5, and the magnesium compound in terms of Mg element with IVB The molar ratio of the chemical treatments of race's elemental metal is 1: 0.01-1, preferably 1: 0.01-0.50, more preferable 1: 0.10- 0.30。

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 Group IVB 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 Group IVB 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

Magnesium compound uses anhydrous magnesium chloride, and porous carrier uses silica, i.e. silica gel, model Ineos company ES757.Silica gel is persistently roasted to 4h under 600 DEG C, nitrogen atmosphere first and thermal activation.Alcohol uses butanol, dissolves magnesium compound Solvent use tetrahydrofuran, Nonmetallocene ligand use structural formula forCompound, sink Shallow lake agent is hexane, and chemical treatments use titanium tetrachloride.

Weigh 2.5g magnesium compound anhydrous magnesium chloride (MgCl₂), a certain amount of butanol and tetrahydrofuran is added, is heated to 60 DEG C dissolution after, continuation be completely dissolved in 60 DEG C of stirrings, be added silica gel formed mixed serum, stir 2h after, addition precipitating reagent hexane It being allowed to precipitate, filter, wash 2 times, each precipitating reagent dosage is identical as additional amount before,

Sediment obtained is at 50 DEG C of temperature (being lower than 15.4 DEG C of solvent boiling point), in the true of absolute pressure 5mBar The lower dry 12h of sky, then at 90 DEG C of temperature (being above the boiling point 24.6 DEG C), the dry 8h under the vacuum of absolute pressure 5mBar Complex carrier is made, wherein alcohol content is 1.6wt%.

25ml hexane solvent is measured, is added in complex carrier, is added dropwise to titanium tetrachloride with 15min under agitation (TiCl₄) chemical treatments, after reacting 4h at 30 DEG C, filtering, hexane is washed 3 times, each 25ml, obtains modifying compound load Body.

25ml hexane solvent is measured, is added in modification complex carrier, Nonmetallocene ligand is added under agitation, After reacting 4h at 30 DEG C, filtering, hexane is washed 3 times, each 25ml, and last vacuum drying obtains load type non-metallocene catalysis Agent.

Proportion are as follows: magnesium compound is 1: 0.5 with butanol molar ratio；The tetrahydrofuran of magnesium compound and dissolution magnesium compound is molten Agent proportion is 1mol: 200ml；The molar ratio of magnesium compound and Nonmetallocene ligand is 1: 0.004；Magnesium compound and porous carrier The quality proportioning 1: 2 of silica gel；The ratio between precipitating reagent hexane and the tetrahydrofuran solvent volume of dissolution magnesium compound are 1: 1；Magnesium chemical combination Object and chemical treatments titanium tetrachloride and molar ratio be 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:

Nonmetallocene ligand is changed into just like with the Nonmetallocene complex of flowering structure.

Wherein: magnesium compound is 1: 0.10 with Nonmetallocene complex molar ratio；

The catalyst is denoted as CAT-2.

Embodiment 3

Before the chemical treatments processing complex carrier, with selected from triethyl aluminum (Al (C₂H₅)₃) help chemical treatment Agent pre-processes the complex carrier.

25ml hexane solvent is measured, is added in the obtained complex 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 obtain pretreated complex 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:

By the mixed serum than 25.4 DEG C of low boiling point of the solvent at a temperature of absolute pressure 5mBar vacuum Lower dry 16h, then high 34.6 DEG C of the boiling point than the solvent at a temperature of, it is dry under the vacuum of absolute pressure 5mBar Complex carrier is made in 10h, and wherein alcohol content is 1.4wt%.

The catalyst is denoted as CAT-4.

Comparative example A

Mixed serum 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 120 DEG C (being higher than 54.6 DEG C of solvent boiling point), absolute Drying obtains complex carrier for 24 hours under the vacuum of pressure 5mBar, and wherein alcohol content is 0.02wt%.

Catalyst is denoted as CAT-A.

Comparative example B

Sediment obtained 20 DEG C (be lower than 45.4 DEG C of solvent boiling point) at a temperature of, in the true of absolute pressure 5mBar The lower dry 12h of sky, obtains complex carrier, wherein alcohol content is 3.5wt%.

Catalyst is denoted as CAT-B.

Embodiment 3 (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, so 20mg load type non-metallocene catalyst and catalyst mixture are added afterwards, adds hydrogen to 0.2MPa, finally persistently leads to Entering ethylene keeps polymerization stagnation pressure constant in 0.8MPa.After reaction, gas reactor is vented, kettle interpolymer is released, after dry Weigh 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 The obtained catalyst of content of alcohol in complex carrier, catalytic activity, polymer stacks density and superelevation point are controlled in the process The performances such as sub- weight northylen viscosity average molecular weigh are superior to complex 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:

Make optionally to mix by the porous carrier that thermal activation treatment and/or chemical activation are handled with the magnesium compound solution, obtain The step of obtaining mixed serum；

The step of handling the complex carrier with the chemical treatments selected from Group IVB metallic compound, obtaining modification complex carrier； With

The modification complex carrier is handled with Nonmetallocene ligand or Nonmetallocene complex, obtains the non-cyclopentadienyl gold of the support type The step of metal catalyst.

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

3. preparation method described in accordance with the claim 1, which is characterized in that the porous carrier is selected from olefin homo or copolymerization Object, polyvinyl alcohol or its copolymer, cyclodextrin, polyester or copolyesters, polyamide or copolyamide, ryuron or copolymerization Object, Voncoat R 3310 or copolymer, methacrylate homopolymer or copolymer, styrene homopolymers or copolymer, this The refractory oxides of the partial cross-linked form of a little homopolymers or copolymer, the periodic table of elements IIA, IIIA, IVA or Group IVB metal Or one of infusibility composite oxides, clay, molecular sieve, mica, montmorillonite, bentonite and diatomite or a variety of, preferably select From partial cross-linked styrene polymer, silica, aluminium oxide, magnesia, oxidation sial, oxidation magnalium, titanium dioxide, divide One of son sieve and montmorillonite are a variety of, are more preferably selected from silica.

4. 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.

5. 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.

6. 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:

7. preparation method according to claim 6, 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.

8. preparation method described in accordance with the claim 1, which is characterized in that the Nonmetallocene complex, which is selected from, has followingization Learn one of compound of structural formula or a variety of:

In above all of chemical structural formula,

Q is 0 or 1；

D is 0 or 1；

M is 1,2 or 3；

M is selected from periodic table of elements III-th family to the central metal atom of X I race metallic atom, and preferably group ivb metal is former Son, more preferable Ti (IV) and Zr (IV)；

N is 1,2,3 or 4, the valence state depending on the central metal atom M；

X is selected from halogen, hydrogen atom, C₁-C₃₀Alkyl, substituted C₁-C₃₀Alkyl, nitrogen-containing group, sulfur-containing group, contains oxygen-containing group Boron group, group containing aluminium base, phosphorus-containing groups, silicon-containing group, germanic group contain tin group, and multiple X can be identical, can also not It together, can also bonding or cyclization each other；

Y is selected from oxygen atom, 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；

→ represent singly-bound or double bond；

Represent covalent bond or ionic bond；

--- represent coordinate bond, covalent bond or ionic bond；

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 or 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, N, O, S, P and Se in R5 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 complex is further preferably selected from one of compound with following chemical structural formula or a variety of:

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

9. preparation method according to claim 8, which is characterized in that

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

The boron-containing group is selected from BF₄ ^-、(C₆F₅)₄B^-Or (R⁴⁰BAr₃)^-；

The group containing aluminium base is selected from alkyl aluminum, AlPh₄ ^-、AlF₄ ^-、AlCl₄ ^-、AlBr₄ ^-、AlI₄ ^-Or R⁴¹AlAr₃ ^-；

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

The Ar represents C₆-C₃₀Aryl；

R⁴⁰To R⁵⁴It is each independently selected from hydrogen, aforementioned C₁-C₃₀Alkyl or aforementioned substituted C₁-C₃₀Alkyl, wherein these groups 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.

10. 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 The molar ratio of Nonmetallocene complex is 1: 0.01-1, preferably 1: 0.04-0.4, more preferable 1: 0.08-0.2, in terms of Mg element The molar ratio of the magnesium compound and the Nonmetallocene ligand is 1: 0.0001-1, preferably 1: 0.0002-0.4, more preferable 1: 0.0008-0.2, further preferred 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 magnesium compound and institute in terms of Mg element The molar ratio for stating alcohol is 1: 0.02~4.00, preferably 1: 0.05~3.00, more preferable 1: 0.10~2.50, with magnesium compound solid The magnesium compound of meter and the mass ratio of the porous carrier are 1: 0.1-20, preferably 1: 0.5-10, more preferable 1: 1-5, institute The volume ratio for stating precipitating reagent and the solvent is 1: 0.2~5, preferably 1: 0.5~2, more preferable 1: 0.8~1.5, and with Mg member Element meter the magnesium compound with the molar ratio of the chemical treatments of Group IVB elemental metal be 1: 0.01-1, preferably 1 : 0.01-0.50, more preferable 1: 0.10-0.30.

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

12. 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.

13. 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.

14. preparation method described in accordance with the claim 1, which is characterized in that the precipitating reagent is selected from alkane, cycloalkane, halogenated One of alkane and halogenated cycloalkane are a variety of, be preferably selected from pentane, hexane, heptane, octane, nonane, decane, hexamethylene, Pentamethylene, cycloheptane, cyclodecane, cyclononane, methylene chloride, dichloro hexane, two chloroheptanes, chloroform, trichloroethanes, trichlorine Butane, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane, three bromobutane, chlorocyclopentane, chloro ring Hexane, chloro cycloheptane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo ring One of heptane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane are a variety of, further preferably selected from hexane, heptane, One of decane and hexamethylene are a variety of, most preferably hexane.

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

By the mixed serum 5-40 DEG C lower than the solvent boiling point at a temperature of, it is 10-30 DEG C preferably low, in absolute pressure 2- Under the vacuum of 100mBar, preferably 5-50mBar, dry 2-48h, preferably 4-24h, then from the solvent boiling point to than described At a temperature of high 50 DEG C of solvent boiling point, preferably from the solvent boiling point at a temperature of 40 DEG C higher than the solvent boiling point, exhausted To under the vacuum of pressure 2-100mBar, preferably 5-50mBar, dry 1-24h, preferably 2-12h obtain the complex carrier,

Alternatively, precipitating reagent is added into the mixed serum, by sediment obtained (optionally after wash) than described It is 10-30 DEG C preferably low at a temperature of solvent boiling point is 5-40 DEG C low, under the vacuum of absolute pressure 2-100mBar, preferably 5- 50mBar, dry 2-48h, preferably 4-24h, then from the solvent boiling point to 50 DEG C of temperature higher than the solvent boiling point Under, preferably from the solvent boiling point at a temperature of 40 DEG C higher than the solvent boiling point, in the vacuum of absolute pressure 2-100mBar Under, preferably 5-50mBar, dry 1-24h, preferably 2-12h obtain the complex carrier.

16. a kind of load type non-metallocene catalyst, it is by according to the described in any item preparation method systems of claim 1-15 It makes.

17. a kind of olefine polymerizing process, which is characterized in that including being urged with load type non-metallocene according to claim 16 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.