CN102059150A - Loaded non-metallocene catalyst and preparation method and application thereof - Google Patents

Abstract

The invention relates to a loaded non-metallocene catalyst and a preparation method and application thereof. The loaded non-metallocene catalyst has the characteristics of simple and practicable preparation method, flexible and adjustable polymerization activity and the like. The invention also relates to the application of the loaded non-metallocene catalyst to the homopolymerisation/copolymerization of olefin. Compared with the prior art, the application has the characteristic of small using amount of a cocatalyst.

Description

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

Technical field

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

Background technology

The non-metallocene catalyst that middle and later periods nineteen nineties occurs, claim luxuriant rear catalyst again, the central atom of major catalyst has comprised nearly all transition metal, reach at some aspect of performance, even surpass metallocene catalyst, become after Ziegler, Ziegler-Natta and metallocene catalyst the 4th generation olefin polymerization catalysis.By the function admirable of the polyolefin products of such catalyst manufacturing, and low cost of manufacture.The non-metallocene catalyst coordination atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger electrophilicity, and have cis alkyl or halogen metal division center, carry out alkene insertion and σ-key easily and shift, the easy alkylation of central metal helps the generation at cation activity center; The complex that forms has the geometric configuration of qualification, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key polarizes easily, more helps the polymerization and the combined polymerization of alkene.Therefore, even under higher polymeric reaction temperature, also can obtain the olefin polymer of higher molecular weight.

But homogeneous catalyst has been proved it in olefinic polyreaction has active duration short, sticking still, high MAO consumption easily, and obtain the too low or too high weak point of polymer molecular weight, only can be used for solution polymerization process or high-pressure polymerization process, seriously limit its industrial applicability.

Patent ZL 01126323.7, ZL 02151294.9ZL 02110844.7 and WO03/010207 disclose a kind of alkene homopolymerization/catalyst for copolymerization or catalyst system and catalyzing, has alkene homopolymerization/copolymerization performance widely, but need higher co-catalyst consumption during in olefinic polymerization at the disclosed catalyst of this patent or catalyst system and catalyzing, could obtain suitable olefin polymerizating activity, and it is short to exist active duration in the polymerization process, phenomenons such as the sticking still of polymer.

Common way be with non-metallocene catalyst by certain load technology, make loaded catalyst, thereby improve the polymerization of alkene and the particle shape of resulting polymers.It shows as the initial activity that has suitably reduced catalyst to a certain extent, prolong the polymerization activity life-span of catalyst, reduce even avoided caking or the poly-cruelly phenomenon in the polymerization process, improve the form of polymer, improve the apparent density of polymer, can make it satisfy more polymerization technique process, as gas-phase polymerization or slurry polymerization etc.

At patent ZL 01126323.7, ZL 02151294.9 ZL 02110844.7 and the disclosed non-metallocene catalyst of WO03/010207, patent CN 1539855A, CN1539856A, CN 1789291A, CN 1789292A, CN 1789290A, WO/2006/063501,200510119401.x carry out load to obtain load type non-metallocene catalyst Deng multiple mode is provided, but these patents all relate on the carrier after the Nonmetallocene organo-metallic compound that will contain transition metal is carried on processing, and because the reaction bonded of non-metallocene catalyst and porous carrier is limited, the Nonmetallocene organic compound mainly is to exist with the physical absorption attitude in the load type non-metallocene catalyst that obtains, and is unfavorable for the control of polymer beads form and the performance of non-metallocene catalyst performance.

Existing olefin polymerization catalysis patent is mostly based on metallocene catalyst, as US4808561, US 5240894, CN 1049439, CN 1136239, CN 1344749, CN1126480, CN1053673, CN 1307594, CN 1130932, CN 1103069, CN1363537, CN 1060179, US 574417, EP 685494, US 4871705 and EP0206794 etc., but these patents also all relate on the carrier after the metallocene catalyst that will contain transition metal is carried on processing.

Patent EP708116 discloses the zirconium chloride that makes gasification earlier and has contacted and load with carrier under 160～450 ℃ of temperature, again that load is good zirconium chloride obtains carried metallocene catalyst with the lithium salts reaction of part, then by cooperate the polymerization that is used for alkene with co-catalyst.The problem that this catalyst exists is that load process requires high temperature, and high vacuum is difficult to be applicable to industrial production.

Patent ZL01131136.3 discloses a kind of method of synthetic carried metallocene catalyst, and carrier is mixed in solvent with IVB group 4 transition metal halide, in direct and part anion reaction.Thereby the synthetic and loadization that realizes metallocene catalyst was finished in a step.But it is 1: 1 that this method requires the transition metal and the mol ratio of part, and needs adding proton donor, and as butyl lithium etc., and the part that is adopted is the metallocene part that contains cyclopentadienyl group of bridging type or non-bridging type.

Patent CN200510080210.7 discloses synthetic supported type vanadium non-metallocene catalyst and preparation and the application of original position; it forms acyl group naphthols magnesium or beta-diketon magnesium compound with dialkyl magnesium with acyl group naphthols or beta-diketon reaction earlier; chloride with the tetravalence vanadium reacts again, forms carrier and active catalytic components simultaneously.

Patent CN200610026765.8 discloses a class single active center Z-N olefin polymerization catalysis.This catalyst, is handled the back through pretreated carrier (as silica gel), metallic compound (as titanium tetrachloride) and this electron donor and is obtained by adding in magnesium compound (as magnesium chloride)/tetrahydrofuran solution as electron donor with the salicylaldehyde derivatives of the salicylide that contains coordinating group or replacement.

CN200610026766.2 is similar with it, discloses a class and has contained heteroatomic organic compound and the application in Ziegler-Natta catalyst thereof.

Patent CN200710162667, CN200710162676.0 and PCT/CN2008/001739 disclose a kind of magnesium compound load type non-metallocene catalyst and preparation method thereof, it adopts magnesium compound (as magnesium halide, alkyl magnesium, alkoxyl magnesium, alkyl alkoxy magnesium), or magnesium compound passes through chemical treatment, and (inorganic agent is an alkyl aluminum, aluminum alkoxide) the modification magnesium compound that obtains, or the modification magnesium compound that adopts magnesium compound-oxolane-alcohol to obtain through post precipitation is a carrier, successively contact by various combination with active metallic compound with the Nonmetallocene part, and the original position load of finishing;

CN200710162677.5, CN200710162672.2, CN200710162675.6 and the disclosed a kind of load type non-metallocene catalyst of PCT/CN2008/001738 and preparation method thereof, be with complex carrier original position load non-metallocene metal ligand method, adopt different complex carrier preparation methods, successively contact by various combination with active metallic compound with the Nonmetallocene part, and the original position load of finishing;

Even so, the ubiquitous problem of the load type non-metallocene catalyst that exists in the prior art is, with silica gel or contain the carrier of the compound of silica gel as the non-metallocene catalyst load, though the particle kenel of the polymer that can help finally obtaining, but owing to being applicable to that the silica gel cost that load is used is higher, and at first need thermal activation or chemical activation, complex treatment process.

And adopting the carrier of magnesium compound as catalyst, it is with low cost, because the strong interaction between the reactive metal in magnesium compound and the Nonmetallocene part is easy to obtain highly active load type non-metallocene catalyst.

Therefore, present present situation is, still needs a kind of load type non-metallocene catalyst, and its preparation method is simple, is fit to suitability for industrialized production, and can overcomes those problems that exist in the prior art load type non-metallocene catalyst.

Summary of the invention

The inventor through diligent discovering, makes described load type non-metallocene catalyst by using a kind of specific preparation method on the basis of existing technology, just can solve foregoing problems, and finish the present invention thus.

According to the preparation method of this load type non-metallocene catalyst, need not add proton donor and electron donor (such as in this area for this reason and the conventional diether compounds that uses) etc., also need not harsh reaction requirement and reaction condition.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.

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

1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:

Magnesium compound and Nonmetallocene part are dissolved in the solvent, obtain the step of magnesium compound solution;

In described magnesium compound solution, add precipitating reagent, obtain to modify the step of carrier; With

Handle described modification carrier with the chemical treatments that is selected from IVB family metallic compound, obtain the step of described load type non-metallocene catalyst.

2. according to each described preparation method of aforementioned aspect, also be included in and adopt described chemical treatments to handle before the described modification carrier, with being selected from aikyiaiurnirsoxan beta, alkyl aluminum or its step that helps the described modification carrier of chemical treatments preliminary treatment that makes up arbitrarily.

3. according to each described preparation method of aforementioned aspect, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide, alkoxyl magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and the alkyl alkoxy magnesium, be preferably selected from the magnesium halide one or more, more preferably magnesium chloride.

4. according to each described preparation method of aforementioned aspect, it is characterized in that described solvent is selected from C _6-12Aromatic hydrocarbon, halo C _6-12In aromatic hydrocarbon, ester and the ether one or more are preferably selected from C _6-12In aromatic hydrocarbon and the oxolane one or more, most preferably oxolane.

5. according to each described preparation method of aforementioned aspect, it is characterized in that described Nonmetallocene part is selected from one or more in the compound with following chemical structural formula:

Be preferably selected from compound (A) with following chemical structural formula and in the compound (B) one or more:

More preferably be selected to compound (A-4) and compound (B-1) to compound (B-4) one or more of compound (A-1) with following chemical structural formula:

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

A be selected from oxygen atom, sulphur atom, selenium atom, -NR ²³R ²⁴,-N (O) R ²⁵R ²⁶,

-PR ²⁸R ²⁹,-P (O) R ³⁰OR ³¹, sulfuryl, sulfoxide group or-Se (O) R ³⁹, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C ₁-C ₃₀Alkyl;

D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C ₁-C ₃₀Alkyl, sulfuryl, sulfoxide group, -N (O) R ²⁵R ²⁶,

Or-P (O) R ³²(OR ³³), N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

G is selected from C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group;

Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

→ represent singly-bound or two key;

-represent covalent bond or ionic bond;

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from hydrogen, C independently of one another ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, is preferably formed aromatic ring; And

R ⁵Be selected from lone pair electrons on the nitrogen, hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R ⁵For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R ⁵In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family metallic atom,

Described Nonmetallocene part further is preferably selected from one or more in the compound with following chemical structural formula:

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

6. according to each described preparation method of aforementioned aspect, it is characterized in that,

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

Described nitrogen-containing group is selected from

-NR ²³R ²⁴,-T-NR ²³R ²⁴Or-N (O) R ²⁵R ²⁶

Described phosphorus-containing groups is selected from

-PR ²⁸R ²⁹,-P (O) R ³⁰R ³¹Or-P (O) R ³²(OR ³³);

Described oxy radical be selected from hydroxyl ,-OR ³⁴With-T-OR ³⁴

Described sulfur-containing group is selected from-SR ³⁵,-T-SR ³⁵,-S (O) R ³⁶Or-T-SO ₂R ³⁷

The described seleno group that contains is selected from-SeR ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹Or-T-Se (O) R ³⁹

Described group T is selected from C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group;

Described R ³⁷Be selected from hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group;

Described C ₁-C ₃₀Alkyl is selected from C ₁-C ₃₀Alkyl, C ₇-C ₅₀Alkaryl, C ₇-C ₅₀Aralkyl, C ₃-C ₃₀Cyclic alkyl, C ₂-C ₃₀Thiazolinyl, C ₂-C ₃₀Alkynyl, C ₆-C ₃₀Aryl, C ₈-C ₃₀Condensed ring radical or C ₄-C ₃₀Heterocyclic radical, wherein said heterocyclic radical contain 1-3 hetero atom that is selected from nitrogen-atoms, oxygen atom or sulphur atom;

The C of described replacement ₁-C ₃₀Alkyl is selected from and has one or more aforementioned halogens or aforementioned C ₁-C ₃₀Alkyl is as substituent aforementioned C ₁-C ₃₀Alkyl;

Described safing function group is selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, contains tin group, C ₁-C _I0Ester group and nitro,

Wherein, described silicon-containing group is selected from-SiR ⁴²R ⁴³R ⁴⁴Or-T-SiR ⁴⁵Described germanic group is selected from-GeR ⁴⁶R ⁴⁷R ⁴⁸Or-T-GeR ⁴⁹Describedly contain tin group and be selected from-SnR ⁵⁰R ⁵¹R ⁵²,-T-SnR ⁵³Or-T-Sn (O) R ⁵⁴And described R ⁴²To R ⁵⁴Be selected from hydrogen, aforementioned C independently of one another ₁-C ₃₀The C of alkyl, aforementioned replacement ₁-C ₃₀Alkyl or aforementioned safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and described group T ditto defines.

7. according to each described preparation method of aforementioned aspect, it is characterized in that, in the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene part is 1: 0.0001-1, preferred 1: 0.0002-0.4, more preferably 1: 0.0008-0.2, further preferred 1: 0.001-0.1, the ratio of described magnesium compound and described solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml, the volume ratio of described precipitating reagent and described solvent is 1: 0.2～5, preferred 1: 0.5～2, more preferably 1: 0.8～1.5, and be 1 in the described magnesium compound of Mg element with mol ratio in the described chemical treatments of IVB family metallic element: 0.01-1, preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30.

8. according to each described preparation method of aforementioned aspect, it is characterized in that, described precipitating reagent is selected from alkane, cycloalkane, in halogenated alkane and the halo cycloalkane one or more, be preferably selected from pentane, hexane, heptane, octane, nonane, decane, cyclohexane, pentamethylene, cycloheptane, cyclodecane, cyclononane, carrene, dichloro hexane, two chloroheptanes, chloroform, trichloroethanes, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane, three NBBs, chlorocyclopentane, chlorocyclohexane, the chloro cycloheptane, the chloro cyclooctane, the chloro cyclononane, the chloro cyclodecane, bromocyclopentane, bromocyclohexane, the bromo cycloheptane, the bromo cyclooctane, in bromo cyclononane and the bromo cyclodecane one or more, further be preferably selected from hexane, heptane, in decane and the cyclohexane one or more, most preferably hexane.

9. according to each described preparation method of aforementioned aspect, it is characterized in that, described IVB family metallic compound is selected from one or more in IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, IVB family metal alkyl halides and the IVB family metal alkoxide halide, be preferably selected from the IVB family metal halide one or more, more preferably be selected from TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄And HfBr ₄In one or more, most preferably be selected from TiCl ₄And ZrCl ₄In one or more.

10. according to each described preparation method of aforementioned aspect, it is characterized in that, described aikyiaiurnirsoxan beta is selected from MAO, the ethyl aikyiaiurnirsoxan beta, in isobutyl aluminium alkoxide and the normal-butyl alumina alkane one or more, more preferably be selected from MAO and the isobutyl aluminium alkoxide one or more, and described alkyl aluminum is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminium, three n-pentyl aluminium, three hexyl aluminium, three isohesyl aluminium, in diethylmethyl aluminium and the dimethyl ethyl aluminium one or more, be preferably selected from trimethyl aluminium, triethyl aluminum, in tri-propyl aluminum and the triisobutyl aluminium one or more most preferably are selected from triethyl aluminum and the triisobutyl aluminium one or more.

It 11., it is characterized in that, is 1 with helping the mol ratio of chemical treatments: 0-1.0, preferred 1: 0-0.5, more preferably 1: 0.1-0.5 in Al element described in the described magnesium compound of Mg element according to each described preparation method of aforementioned aspect.

12. a load type non-metallocene catalyst, it is by making according to each described preparation method of aforementioned aspect.

13. alkene homopolymerization/copolymerization process, it is characterized in that, being major catalyst according to aforementioned aspect 12 described load type non-metallocene catalysts, to be selected from aikyiaiurnirsoxan beta, alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is co-catalyst, makes alkene homopolymerization or copolymerization.

Technique effect

Preparation method's technology simple possible of load type non-metallocene catalyst of the present invention, and the load capacity of Nonmetallocene part is adjustable, can give full play to it and obtain the performance of polyolefin product, thereby and can regulate molecular weight distribution and ultra-high molecular weight polyethylene viscosity average molecular weigh by the difference of regulating addition at catalysis in olefine polymerization.

By adopting different chemical treatments consumptions, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst, adapt to different olefinic polymerization requirements thus, thereby and can cooperate the preparation process of the addition of Nonmetallocene part that catalyst and polymer performance are regulated.

Adopt method for preparing catalyst provided by the invention, fully obtaining after the post precipitation filtration washing drying under the precipitating reagent effect by magnesium compound solution owing to modify carrier, so the combination of key substance is comparatively tight in the catalyst.

In addition, the present invention finds, adopt to handle with co-catalyst earlier and modify carrier, and then handle resulting load type non-metallocene catalyst with chemical treatments, with only handle resulting load type non-metallocene catalyst and compare with chemical treatments, catalytic activity and polymer stacks density are higher, and molecular weight distribution is narrower, and the ultra-high molecular weight polyethylene viscosity average molecular weigh is higher.

Also find simultaneously, when employing load type non-metallocene catalyst that the present invention obtained and co-catalyst constitute catalyst system and catalyzing, only need fewer co-catalyst (such as MAO or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity, show comonomer effect significantly during copolymerization, promptly under equal relatively condition, the copolymerization activity is higher than the homopolymerization activity, and has good polymer morphology and high polymer bulk density by polymer such as catalyzed alkene homopolymerization or the resulting polyethylene of copolymerization.

The specific embodiment

Below the specific embodiment of the present invention is elaborated, but it is pointed out that protection scope of the present invention is not subjected to the restriction of these specific embodiment, but determine by claims of appendix.

According to the present invention, relate to a kind of preparation method of load type non-metallocene catalyst, may further comprise the steps: magnesium compound and Nonmetallocene part are dissolved in the solvent, obtain the step of magnesium compound solution; In described magnesium compound solution, add precipitating reagent, obtain to modify the step of carrier; With handle described modification carrier with the chemical treatments that is selected from IVB family metallic compound, obtain the step of described load type non-metallocene catalyst.

Below the step that obtains described magnesium compound solution is carried out specific description.

Particularly, make described magnesium compound (solid) and described Nonmetallocene part be dissolved in appropriate solvent (promptly being used for dissolving the solvent of described magnesium compound), thereby obtain described magnesium compound solution.

As described solvent, such as enumerating C _6-12Aromatic hydrocarbon, halo C _6-12Aromatic hydrocarbon, ester and ether equal solvent.Specifically such as enumerating toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, ethyl acetate and oxolane etc.Wherein, preferred C _6-12Aromatic hydrocarbon and oxolane, most preferably oxolane.

These solvents can be used alone, and also can use with the multiple mixing of ratio arbitrarily.

In order to prepare described magnesium compound solution, described magnesium compound and the metering of described Nonmetallocene part added to dissolve in the described solvent to getting final product.

When the described magnesium compound solution of preparation, ratio in the described magnesium compound (solid) of magnesium elements and the described solvent that is used to dissolve described magnesium compound is generally 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml.

According to the present invention, as the consumption of described Nonmetallocene part, make to reach 1: 0.0001-1, preferred 1: 0.0002-0.4 in the described magnesium compound (solid) of Mg element and the mol ratio of described Nonmetallocene part, more preferably 1: 0.0008-0.2, further preferred 1: 0.001-0.1.

There is no particular limitation to the preparation time (being the dissolution time of described magnesium compound and described Nonmetallocene part) of described magnesium compound solution, but be generally 0.5～24h, preferred 4～24h.In this preparation process, can utilize and stir the dissolving that promotes described magnesium compound and described Nonmetallocene part.This stirring can be adopted any form, such as paddle (rotating speed is generally 10～1000 rev/mins) etc.As required, can promote dissolving sometimes by suitable heating.

Below described magnesium compound is carried out specific description.

According to the present invention, term " magnesium compound " uses the common notion in this area, refers to as the conventional organic or inorganic solid water-free magnesium-containing compound that uses of the carrier of supported olefin polymerization catalyst.

According to the present invention, as described magnesium compound, such as enumerating magnesium halide, alkoxyl magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium.

Particularly, as described magnesium halide, such as enumerating magnesium chloride (MgCl ₂), magnesium bromide (MgBr ₂), magnesium iodide (MgI ₂) and magnesium fluoride (MgF ₂) etc., wherein preferred magnesium chloride.

As described alkoxyl magnesium halide, such as enumerating methoxyl group chlorination magnesium (Mg (OCH ₃) Cl), ethyoxyl magnesium chloride (Mg (OC ₂H ₅) Cl), propoxyl group magnesium chloride (Mg (OC ₃H ₇) Cl), n-butoxy magnesium chloride (Mg (OC ₄H ₉) Cl), isobutoxy magnesium chloride (Mg (i-OC ₄H ₉) Cl), methoxyl group magnesium bromide (Mg (OCH ₃) Br), ethyoxyl magnesium bromide (Mg (OC ₂H ₅) Br), propoxyl group magnesium bromide (Mg (OC ₃H ₇) Br), n-butoxy magnesium bromide (Mg (OC ₄H ₉) Br), isobutoxy magnesium bromide (Mg (i-OC ₄H ₉) Br), methoxyl group magnesium iodide (Mg (OCH ₃) I), ethyoxyl magnesium iodide (Mg (OC ₂H ₅) I), propoxyl group magnesium iodide (Mg (OC ₃H ₇) I), n-butoxy magnesium iodide (Mg (OC ₄H ₉) I) and isobutoxy magnesium iodide (Mg (i-OC ₄H ₉) I) etc., wherein preferred methoxyl group chlorination magnesium, ethyoxyl magnesium chloride and isobutoxy magnesium chloride.

As described alkoxyl magnesium, such as enumerating magnesium methoxide (Mg (OCH ₃) ₂), magnesium ethylate (Mg (OC ₂H ₅) ₂), propoxyl group magnesium (Mg (OC ₃H ₇) ₂), butoxy magnesium (Mg (OC ₄H ₉) ₂), isobutoxy magnesium (Mg (i-OC ₄H ₉) ₂) and ₂-ethyl hexyl oxy magnesium (Mg (OCH ₂CH (C ₂H ₅) C ₄H) ₂) etc., wherein preferred magnesium ethylate and isobutoxy magnesium.

As described alkyl magnesium, such as enumerating methyl magnesium (Mg (CH ₃) ₂), magnesium ethide (Mg (C ₂H ₅) ₂), propyl group magnesium (Mg (C ₃H ₇) ₂), normal-butyl magnesium (Mg (C ₄H ₉) ₂) and isobutyl group magnesium (Mg (i-C ₄H ₉) ₂) etc., wherein preferred magnesium ethide and normal-butyl magnesium.

As described alkyl halide magnesium, such as enumerating methyl-magnesium-chloride (Mg (CH ₃) Cl), ethylmagnesium chloride (Mg (C ₂H ₅) Cl), propyl group magnesium chloride (Mg (C ₃H ₇) Cl), normal-butyl chlorination magnesium (Mg (C ₄H ₉) Cl), isobutyl group chlorination magnesium (Mg (i-C ₄H ₉) Cl), methyl-magnesium-bromide (Mg (CH ₃) Br), ethylmagnesium bromide (Mg (C ₂H ₅) Br), propyl group magnesium bromide (Mg (C ₃H ₇) Br), normal-butyl bromination magnesium (Mg (C ₄H ₉) Br), isobutyl group bromination magnesium (Mg (i-C ₄H ₉) Br), methyl magnesium iodide (Mg (CH ₃) I), ethyl magnesium iodide (Mg (C ₂H ₅) I), propyl group magnesium iodide (Mg (C ₃H ₇) I), normal-butyl iodate magnesium (Mg (C ₄H ₉) I) and isobutyl group iodate magnesium (Mg (i-C ₄H ₉) I) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl group chlorination magnesium.

As described alkyl alkoxy magnesium, such as enumerating methyl methoxy base magnesium (Mg (OCH ₃) (CH ₃)), methyl ethoxy magnesium (Mg (OC ₂H ₅) (CH ₃)), methyl propoxyl group magnesium (Mg (OC ₃H ₇) (CH ₃)), methyl n-butoxy magnesium (Mg (OC ₄H ₉) (CH ₃)), methyl isobutoxy magnesium (Mg (i-OC ₄H ₉) (CH ₃)), ethyl magnesium methoxide (Mg (OCH ₃) (C ₂H ₅)), ethyl magnesium ethylate (Mg (OC ₂H ₅) (C ₂H ₅)), ethyl propoxyl group magnesium (Mg (OC ₃H ₇) (C ₂H ₅)), ethyl n-butoxy magnesium (Mg (OC ₄H ₉) (C ₂H ₅)), ethyl isobutoxy magnesium (Mg (i-OC ₄H ₉) (C ₂H ₅)), propyl group magnesium methoxide (Mg (OCH ₃) (C ₃H ₇)), propyl group magnesium ethylate (Mg (OC ₂H ₅) (C ₃H ₇)), propyl group propoxyl group magnesium (Mg (OC ₃H ₇) (C ₃H ₇)), propyl group n-butoxy magnesium (Mg (OC ₄H ₉) (C ₃H ₇)), propyl group isobutoxy magnesium (Mg (i-OC ₄H ₉) (C ₃H ₇)), normal-butyl magnesium methoxide (Mg (OCH ₃) (C ₄H ₉)), normal-butyl magnesium ethylate (Mg (OC ₂H ₅) (C ₄H ₉)), normal-butyl propoxyl group magnesium (Mg (OC ₃H ₇) (C ₄H ₉)), normal-butyl n-butoxy magnesium (Mg (OC ₄H ₉) (C ₄H ₉)), normal-butyl isobutoxy magnesium (Mg (i-OC ₄H ₉) (C ₄H ₉)), isobutyl group magnesium methoxide (Mg (OCH ₃) (i-C ₄H ₉)), isobutyl group magnesium ethylate (Mg (OC ₂H ₅) (i-C ₄H ₉)), isobutyl group propoxyl group magnesium (Mg (OC ₃H ₇) (i-C ₄H ₉)), isobutyl group n-butoxy magnesium (Mg (OC ₄H ₉) (i-C ₄H ₉)) and isobutyl group isobutoxy magnesium (Mg (i-OC ₄H ₉) (i-C ₄H ₉)) etc., wherein preferred butyl magnesium ethylate.

These magnesium compounds can be used alone, and also can multiple mixing use, not special restriction.

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

According to the present invention, term " Nonmetallocene complex " refers to a kind of metallo-organic compound (therefore described Nonmetallocene complex is also sometimes referred to as the non-metallocene olefin polymerization complex) that can demonstrate the olefinic polymerization catalysis activity when making up with aikyiaiurnirsoxan beta, this compound comprises the multidentate ligand (preferably tridentate ligand or more multidentate ligand) that central metal atom and at least one and described central metal atom combine with coordinate bond, and term " Nonmetallocene part " is aforesaid multidentate ligand.

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

According to the present invention, group A, D in this compound and E (coordination group) form coordinate bond by its contained coordination with the contained IVB family metallic atom generation complexation reaction of the IVB family metallic compound that uses as chemical treatments among atom (such as hetero atoms such as N, O, S, Se and P) and the present invention, the complex (being Nonmetallocene complex of the present invention) that to form with this IVB family metallic atom thus be central atom.

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

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

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

A be selected from oxygen atom, sulphur atom, selenium atom, -NR ²³R ²⁴,-N (O) R ²⁵R ²⁶, -PR ²⁸R ²⁹,-P (O) R ³⁰OR ³¹, sulfuryl, sulfoxide group or-Se (O) R ³⁹, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C ₁-C ₃₀Alkyl;

D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C ₁-C ₃₀Alkyl, sulfuryl, sulfoxide group,

-N (O) R ²⁵R ²⁶,

Or-P (O) R ³²(OR ³³), N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

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

F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

G is selected from C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group;

Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyano group (CN), such as enumerating-NR ²³R ²⁴,-N (O) R ²⁵R ²⁶,-PR ²⁸R ²⁹,-P (O) R ³⁰R ³¹,-OR ³⁴,-SR ³⁵,-S (O) R ³⁶,-SeR ³⁸Or-Se (O) R ³⁹, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

→ represent singly-bound or two key;

-represent covalent bond or ionic bond;

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from hydrogen, C independently of one another ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl (wherein preferred halo alkyl, such as-CH ₂Cl and-CH ₂CH ₂Cl) or the safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group is such as R ¹With R ², R ⁶With R ⁷, R ⁷With R ⁸, R ⁸With R ⁹, R ¹³With R ¹⁴, R ¹⁴With R ¹⁵, R ¹⁵With R ¹⁶, R ¹⁸With R ¹⁹, R ¹⁹With R ²⁰, R ²⁰With R ²¹, R ²³With R ²⁴, perhaps R ²⁵With R ²⁶Deng combining togather into key or Cheng Huan, be preferably formed aromatic ring, such as unsubstituted phenyl ring or by 1-4 C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl (wherein preferred halo alkyl, such as-CH ₂Cl and-CH ₂CH ₂Cl) or the phenyl ring that replaces of safing function group; And

R ⁵Be selected from lone pair electrons on the nitrogen, hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R ⁵For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R ⁵In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family metallic atom.

According to the present invention, in aforementioned all chemical structural formulas, as the case may be, any adjacent two or more groups are such as R ²¹With group Z, perhaps R ¹³With group Y, can combine togather into ring, be preferably formed and comprise the heteroatomic C that comes from described group Z or Y ₆-C ₃₀Heteroaromatic, such as pyridine ring etc., wherein said heteroaromatic is optional to be selected from C by one or more ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀The substituting group of alkyl and safing function group replaces.

In the context of the present invention,

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

Described nitrogen-containing group is selected from

-NR ²³R ²⁴,-T-NR ²³R ²⁴Or-N (O) R ²⁵R ²⁶

Described phosphorus-containing groups is selected from

-PR ²⁸R ²⁹,-P (O) R ³⁰R ³¹Or-P (O) R ³²(OR ³³);

Described oxy radical be selected from hydroxyl ,-OR ³⁴With-T-OR ³⁴

Described sulfur-containing group is selected from-SR ³⁵,-T-SR ³⁵,-S (O) R ³⁶Or-T-SO ₂R ³⁷

The described seleno group that contains is selected from-SeR ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹Or-T-Se (O) R ³⁹

Described group T is selected from C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group; With

Described R ³⁷Be selected from hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group.

In the context of the present invention, described C ₁-C ₃₀Alkyl is selected from C ₁-C ₃₀Alkyl (preferred C ₁-C ₆Alkyl is such as isobutyl group), C ₇-C ₅₀Alkaryl (such as tolyl, xylyl, diisobutyl phenyl etc.), C ₇-C ₅₀Aralkyl (such as benzyl), C ₃-C ₃₀Cyclic alkyl, C ₂-C ₃₀Thiazolinyl, C ₂-C ₃₀Alkynyl, C ₆-C ₃₀Aryl (such as phenyl, naphthyl, anthryl etc.), C ₈-C ₃₀Condensed ring radical or C ₄-C ₃₀Heterocyclic radical, wherein said heterocyclic radical contain 1-3 hetero atom that is selected from nitrogen-atoms, oxygen atom or sulphur atom, such as pyridine radicals, pyrrole radicals, furyl or thienyl etc.

According to the present invention, in the context of the present invention, according to the concrete condition of the relevant group of its combination, described C ₁-C ₃₀Alkyl refers to C sometimes ₁-C ₃₀(divalent group perhaps is called C to hydrocarbon two bases ₁-C ₃₀Alkylene) or C ₁-C ₃₀Hydrocarbon three bases (trivalent group), this is obvious to those skilled in the art.

In the context of the present invention, the C of described replacement ₁-C ₃₀Alkyl refers to the aforementioned C that has one or more inert substituents ₁-C ₃₀Alkyl.So-called inert substituent refers to these substituting groups aforementioned coordination (is referred to aforementioned group A, D, E, F, Y and Z, the perhaps also optional R that comprises with group ⁵) there is not substantial interference with the coordination process of central metal atom (aforementioned IVB family metallic atom); In other words, limit by the chemical constitution of part of the present invention, these substituting groups do not have ability or have no chance (such as the influence that is subjected to steric hindrance etc.) forms coordinate bond with described IVB family's metallic atom generation complexation reaction.Generally speaking, described inert substituent refers to aforementioned halogen or C ₁-C ₃₀Alkyl (preferred C ₁-C ₆Alkyl is such as isobutyl group).

In the context of the present invention, described safing function group does not comprise aforesaid C ₁-C ₃₀The C of alkyl and aforesaid replacement ₁-C ₃₀Alkyl.As described safing function group, such as enumerating aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, containing tin group, C ₁-C ₁₀Ester group and nitro (NO ₂) etc.

In the context of the present invention, limit by the chemical constitution of part of the present invention, described safing function group has following characteristics:

(1) do not disturb described group A, D, E, F, Y or Z and described IVB family metallic atom the coordination process and

(2) coordination ability with described IVB family metallic atom is lower than described A, D, E, F, Y and Z group, and does not replace the existing coordination of these groups and described IVB family metallic atom.

In the context of the present invention, described silicon-containing group is selected from-SiR ⁴²R ⁴³R ⁴⁴Or-T-SiR ⁴⁵Described germanic group is selected from-GeR ⁴⁶R ⁴⁷R ⁴⁸Or-T-GeR ⁴⁹Describedly contain tin group and be selected from-SnR ⁵⁰R ⁵¹R ⁵²,-T-SnR ⁵³Or-T-Sn (O) R ⁵⁴And described R ⁴²To R ⁵⁴Be selected from hydrogen, aforesaid C independently of one another ₁-C ₃₀The C of alkyl, aforesaid replacement ₁-C ₃₀Alkyl or aforesaid safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and the definition of described group T is the same.

As described Nonmetallocene part, such as enumerating following compound:

Wherein, described Nonmetallocene part is preferably selected from following compound:

Described Nonmetallocene part further is preferably selected from following compound:

Described Nonmetallocene part more preferably is selected from following compound:

These Nonmetallocene parts can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.

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

Described Nonmetallocene part can be made according to any method well known by persons skilled in the art.About the particular content of its manufacture method, such as can be referring to WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 etc., the full text that this specification is introduced these documents at this point as a reference.

According to the present invention, by in described magnesium compound solution, being metered into precipitating reagent, solid matter is precipitated out from this magnesium compound solution, obtain to modify carrier thus.

Below described precipitating reagent is carried out specific description.

According to the present invention, term " precipitating reagent " uses the common notion in this area, refers to reduce the solubility of solute (such as described magnesium compound) in its solution and and then chemical inertness liquid state that it is separated out with solid form from described solution.

According to the present invention, as described precipitating reagent, for described magnesium compound, be poor solvent such as enumerating, and for the described solvent that is used to dissolve described magnesium compound, be the solvent of good solvent, such as enumerating alkane, cycloalkane, halogenated alkane and halo cycloalkane.

As described alkane, such as enumerating pentane, hexane, heptane, octane, nonane and decane etc., wherein preferred hexane, heptane and decane, most preferably hexane.

As described cycloalkane, such as enumerating cyclohexane, pentamethylene, cycloheptane, cyclodecane and cyclononane etc., most preferably cyclohexane.

As described halogenated alkane, such as enumerating carrene, dichloro hexane, two chloroheptanes, chloroform, trichloroethanes, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane and three NBBs etc.

As described halo cycloalkane, such as enumerating chlorocyclopentane, chlorocyclohexane, chloro cycloheptane, chloro 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 also can use with the multiple mixing of ratio arbitrarily.

The adding mode of precipitating reagent can be disposable adding or dropping, preferred disposable adding.In this precipitation process, can utilize to stir to promote the dispersion of precipitating reagent in described magnesium compound solution, and help the final precipitation of solid product.This stirring can be adopted any form, such as paddle (rotating speed is generally 10～1000 rev/mins) etc.

There is no particular limitation to the consumption of described precipitating reagent, but generally by volume, and described precipitating reagent is 1: 0.2～5 with the ratio of the described solvent that is used to dissolve described magnesium compound, and preferred 1: 0.5～2, more preferably 1: 0.8～1.5.

Also there is no particular limitation to the temperature of described precipitating reagent, but general preferred normal temperature.And this precipitation process is generally also preferably carried out at normal temperatures.

Post precipitation filters, washs and drying the solid product that is obtained fully.For described filtration, washing and dry not special qualification of method, can use conventional those that use in this area as required.

As required, described washing is generally carried out 1～6 time, preferred 2～3 times.Wherein, washer solvent preferably uses the solvent identical with precipitating reagent, but also can be different.

Described drying can adopt conventional method to carry out, such as heat drying method under inert gas seasoning, boulton process or the vacuum, and heat drying method, most preferably heat drying method under the vacuum under preferred inert gas seasoning or the vacuum.

The temperature range of described drying is generally normal temperature to 100 ℃, exceeds and no longer reduce up to quality of material with drying drying time.Such as, when adopting the oxolane conduct to be used to dissolve the solvent of described magnesium compound, baking temperature is generally about 80 ℃, under vacuum, got final product in dry 2～12 hours, and when adopting the toluene conduct to be used to dissolve the solvent of described magnesium compound, baking temperature is generally about 100 ℃, gets final product in dry 4～24 hours under vacuum.

Then, handle described modification carrier, obtain load type non-metallocene catalyst of the present invention thus with the chemical treatments that is selected from IVB family metallic compound.

According to the present invention, by described modification carrier being carried out chemical treatment with described chemical treatments, Nonmetallocene part contained in described chemical treatments and this modification carrier is reacted, thereby original position generates Nonmetallocene complex (original position load reaction) on carrier, obtains load type non-metallocene catalyst of the present invention thus.

Below described chemical treatments is carried out specific description.

According to the present invention, with IVB family metallic compound as described chemical treatments.

As described IVB family metallic compound, such as enumerating IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, IVB family metal alkyl halides and IVB family metal alkoxide halide.

As described IVB family metal halide, described IVB family metal alkyl compound, described IVB family metal alkoxide compound, described IVB family's metal alkyl halides and described IVB family metal alkoxide halide, such as the compound that can enumerate following general formula (IV) structure:

M(OR ¹) _mX _nR ² _4-m-n (IV)

Wherein:

M is 0,1,2,3 or 4;

N is 0,1,2,3 or 4;

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

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

R ¹And R ²Be selected from C independently of one another _1-10Alkyl is such as methyl, ethyl, propyl group, normal-butyl, isobutyl group etc., R ¹And R ²Can be identical, also can be different.

Particularly, as described IVB family metal halide, such as enumerating titanium tetrafluoride (TiF ₄), titanium tetrachloride (TiCl ₄), titanium tetrabromide (TiBr ₄), titanium tetra iodide (TiI ₄);

Zirconium tetrafluoride (ZrF ₄), zirconium chloride (ZrCl ₄), tetrabormated zirconium (ZrBr ₄), zirconium tetraiodide (ZrI ₄);

Tetrafluoride hafnium (HfF ₄), hafnium tetrachloride (HfCl ₄), hafnium (HfBr ₄), tetraiodide hafnium (HfI ₄).

As described IVB family metal alkyl compound, such as enumerating tetramethyl titanium (Ti (CH ₃) ₄), tetraethyl titanium (Ti (CH ₃CH ₂) ₄), four isobutyl group titanium (Ti (i-C ₄H ₉) ₄), tetra-n-butyl titanium (Ti (C ₄H ₉) ₄), triethyl group methyltitanium (Ti (CH ₃) (CH ₃CH ₂) ₃), diethyl-dimethyl titanium (Ti (CH ₃) ₂(CH ₃CH ₂) ₂), trimethyl ethyl titanium (Ti (CH ₃) ₃(CH ₃CH ₂)), triisobutyl methyltitanium (Ti (CH ₃) (i-C ₄H ₉) ₃), diisobutyl dimethyl titanium (Ti (CH ₃) ₂(i-C ₄H ₉) ₂), trimethyl isobutyl group titanium (Ti (CH ₃) ₃(i-C ₄H ₉)), triisobutyl ethyl titanium (Ti (CH ₃CH ₂) (i-C ₄H ₉) ₃), diisobutyl diethyl titanium (Ti (CH ₃CH ₂) ₂(i-C ₄H ₉) ₂), triethyl group isobutyl group titanium (Ti (CH ₃CH ₂) ₃(i-C ₄H ₉)), three normal-butyl methyltitanium (Ti (CH ₃) (C ₄H ₉) ₃), di-n-butyl dimethyl titanium (Ti (CH ₃) ₂(C ₄H ₉) ₂), trimethyl normal-butyl titanium (Ti (CH ₃) ₃(C ₄H ₉)), three normal-butyl methyltitanium (Ti (CH ₃CH ₂) (C ₄H ₉) ₃), di-n-butyl diethyl titanium (Ti (CH ₃CH ₂) ₂(C ₄H ₉) ₂), triethyl group normal-butyl titanium (Ti (CH ₃CH ₂) ₃(C ₄H ₉)) etc.;

Tetramethyl zirconium (Zr (CH ₃) ₄), tetraethyl zirconium (Zr (CH ₃CH ₂) ₄), four isobutyl group zirconium (Zr (i-C ₄H ₉) ₄), tetra-n-butyl zirconium (Zr (C ₄H ₉) ₄), triethyl group methylcyclopentadienyl zirconium (Zr (CH ₃) (CH ₃CH ₂) ₃), diethyl-dimethyl zirconium (Zr (CH ₃) ₂(CH ₃CH ₂) ₂), trimethyl ethyl zirconium (Zr (CH ₃) ₃(CH ₃CH ₂)), triisobutyl methylcyclopentadienyl zirconium (Zr (CH ₃) (i-C ₄H ₉) ₃), diisobutyl zirconium dimethyl (Zr (CH ₃) ₂(i-C ₄H ₉) ₂), trimethyl isobutyl group zirconium (Zr (CH ₃) ₃(i-C ₄H ₉)), triisobutyl ethyl zirconium (Zr (CH ₃CH ₂) (i-C ₄H ₉) ₃), diisobutyl diethyl zirconium (Zr (CH ₃CH ₂) ₂(i-C ₄H ₉) ₂), triethyl group isobutyl group zirconium (Zr (CH ₃CH ₂) ₃(i-C ₄H ₉)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH ₃) (C ₄H ₉) ₃), di-n-butyl zirconium dimethyl (Zr (CH ₃) ₂(C ₄H ₉) ₂), trimethyl normal-butyl zirconium (Zr (CH ₃) ₃(C ₄H ₉)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH ₃CH ₂) (C ₄H ₉) ₃), di-n-butyl diethyl zirconium (Zr (CH ₃CH ₂) ₂(C ₄H ₉) ₂), triethyl group normal-butyl zirconium (Zr (CH ₃CH ₂) ₃(C ₄H ₉)) etc.;

Tetramethyl hafnium (Hf (CH ₃) ₄), tetraethyl hafnium (Hf (CH ₃CH ₂) ₄), four isobutyl group hafnium (Hf (i-C ₄H ₉) ₄), tetra-n-butyl hafnium (Hf (C ₄H ₉) ₄), triethyl group methylcyclopentadienyl hafnium (Hf (CH ₃) (CH ₃CH ₂) ₃), diethyl-dimethyl hafnium (Hf (CH ₃) ₂(CH ₃CH ₂) ₂), trimethyl ethyl hafnium (Hf (CH ₃) ₃(CH ₃CH ₂)), triisobutyl methylcyclopentadienyl hafnium (Hf (CH ₃) (i-C ₄H ₉) ₃), diisobutyl dimethyl hafnium (Hf (CH ₃) ₂(i-C ₄H ₉) ₂), trimethyl isobutyl group hafnium (Hf (CH ₃) ₃(i-C ₄H ₉)), triisobutyl ethyl hafnium (Hf (CH ₃CH ₂) (i-C ₄H ₉) ₃), diisobutyl diethyl hafnium (Hf (CH ₃CH ₂) ₂(i-C ₄H ₉) ₂), triethyl group isobutyl group hafnium (Hf (CH ₃CH ₂) ₃(i-C ₄H ₉)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH ₃) (C ₄H ₉) ₃), di-n-butyl dimethyl hafnium (Hf (CH ₃) ₂(C ₄H ₉) ₂), trimethyl normal-butyl hafnium (Hf (CH ₃) ₃(C ₄H ₉)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH ₃CH ₂) (C ₄H ₉) ₃), di-n-butyl diethyl hafnium (Hf (CH ₃CH ₂) ₂(C ₄H ₉) ₂), triethyl group normal-butyl hafnium (Hf (CH ₃CH ₂) ₃(C ₄H ₉)) etc.

As described IVB family metal alkoxide compound, such as enumerating tetramethoxy titanium (Ti (OCH ₃) ₄), purity titanium tetraethoxide (Ti (OCH ₃CH ₂) ₄), four isobutoxy titanium (Ti (i-OC ₄H ₉) ₄), four titanium n-butoxide (Ti (OC ₄H ₉) ₄), triethoxy methoxyl group titanium (Ti (OCH ₃) (OCH ₃CH ₂) ₃), diethoxy dimethoxy titanium (Ti (OCH ₃) ₂(OCH ₃CH ₂) ₂), trimethoxy ethanolato-titanium (Ti (OCH ₃) ₃(OCH ₃CH ₂)), three isobutoxy methoxyl group titanium (Ti (OCH ₃) (i-OC ₄H ₉) ₃), two isobutoxy dimethoxy titanium (Ti (OCH ₃) ₂(i-OC ₄H ₉) ₂), trimethoxy isobutoxy titanium (Ti (OCH ₃) ₃(i-OC ₄H ₉)), three isobutoxy ethanolato-titanium (Ti (OCH ₃CH ₂) (i-OC ₄H ₉) ₃), two isobutoxy diethoxy titanium (Ti (OCH ₃CH ₂) ₂(i-OC ₄H ₉) ₂), triethoxy isobutoxy titanium (Ti (OCH ₃CH ₂) ₃(i-OC ₄H ₉)), three n-butoxy methoxyl group titanium (Ti (OCH ₃) (OC ₄H ₉) ₃), two n-butoxy dimethoxy titanium (Ti (OCH ₃) ₂(OC ₄H ₉) ₂), trimethoxy titanium n-butoxide (Ti (OCH ₃) ₃(OC ₄H ₉)), three n-butoxy methoxyl group titanium (Ti (OCH ₃CH ₂) (OC ₄H ₉) ₃), two n-butoxy diethoxy titanium (Ti (OCH ₃CH ₂) ₂(OC ₄H ₉) ₂), triethoxy titanium n-butoxide (Ti (OCH ₃CH ₂) ₃(OC ₄H ₉)) etc.;

Tetramethoxy zirconium (Zr (OCH ₃) ₄), tetraethoxy zirconium (Zr (OCH ₃CH ₂) ₄), four isobutoxy zirconium (Zr (i-OC ₄H ₉) ₄), four n-butoxy zirconium (Zr (OC ₄H ₉) ₄), triethoxy methoxyl group zirconium (Zr (OCH ₃) (OCH ₃CH ₂) ₃), diethoxy dimethoxy zirconium (Zr (OCH ₃) ₂(OCH ₃CH ₂) ₂), trimethoxy ethyoxyl zirconium (Zr (OCH ₃) ₃(OCH ₃CH ₂)), three isobutoxy methoxyl group zirconium (Zr (OCH ₃) (i-OC ₄H ₉) ₃), two isobutoxy dimethoxy zirconium (Zr (OCH ₃) ₂(i-OC ₄H ₉) ₂), trimethoxy isobutoxy zirconium (Zr (OCH ₃) ₃(i-C ₄H ₉)), three isobutoxy ethyoxyl zirconium (Zr (OCH ₃CH ₂) (i-OC ₄H ₉) ₃), two isobutoxy diethoxy zirconium (Zr (OCH ₃CH ₂) ₂(i-OC ₄H ₉) ₂), triethoxy isobutoxy zirconium (Zr (OCH ₃CH ₂) ₃(i-OC ₄H ₉)), three n-butoxy methoxyl group zirconium (Zr (OCH ₃) (OC ₄H ₉) ₃), two n-butoxy dimethoxy zirconium (Zr (OCH ₃) ₂(OC ₄H ₉) ₂), trimethoxy n-butoxy zirconium (Zr (OCH ₃) ₃(OC ₄H ₉)), three n-butoxy methoxyl group zirconium (Zr (OCH ₃CH ₂) (OC ₄H ₉) ₃), two n-butoxy diethoxy zirconium (Zr (OCH ₃CH ₂) ₂(OC ₄H ₉) ₂), triethoxy n-butoxy zirconium (Zr (OCH ₃CH ₂) ₃(OC ₄H ₉)) etc.;

Tetramethoxy hafnium (Hf (OCH ₃) ₄), tetraethoxy hafnium (Hf (OCH ₃CH ₂) ₄), four isobutoxy hafnium (Hf (i-OC ₄H ₉) ₄), four n-butoxy hafnium (Hf (OC ₄H ₉) ₄), triethoxy methoxyl group hafnium (Hf (OCH ₃) (OCH ₃CH ₂) ₃), diethoxy dimethoxy hafnium (Hf (OCH ₃) ₂(OCH ₃CH ₂) ₂), trimethoxy ethyoxyl hafnium (Hf (OCH ₃) ₃(OCH ₃CH ₂)), three isobutoxy methoxyl group hafnium (Hf (OCH ₃) (i-OC ₄H ₉) ₃), two isobutoxy dimethoxy hafnium (Hf (OCH ₃) ₂(i-OC ₄H ₉) ₂), trimethoxy isobutoxy hafnium (Hf (OCH ₃) ₃(i-OC ₄H ₉)), three isobutoxy ethyoxyl hafnium (Hf (OCH ₃CH ₂) (i-OC ₄H ₉) ₃), two isobutoxy diethoxy hafnium (Hf (OCH ₃CH ₂) ₂(i-OC ₄H ₉) ₂), triethoxy isobutoxy hafnium (Hf (OCH ₃CH ₂) ₃(i-C ₄H ₉)), three n-butoxy methoxyl group hafnium (Hf (OCH ₃) (OC ₄H ₉) ₃), two n-butoxy dimethoxy hafnium (Hf (OCH ₃) ₂(OC ₄H ₉) ₂), trimethoxy n-butoxy hafnium (Hf (OCH ₃) ₃(OC ₄H ₉)), three n-butoxy methoxyl group hafnium (Hf (OCH ₃CH ₂) (OC ₄H ₉) ₃), two n-butoxy diethoxy hafnium (Hf (OCH ₃CH ₂) ₂(OC ₄H ₉) ₂), triethoxy n-butoxy hafnium (Hf (OCH ₃CH ₂) ₃(OC ₄H ₉)) etc.

As described IVB family metal alkyl halides, such as enumerating trimethyl titanium chloride (TiCl (CH ₃) ₃), triethyl group titanium chloride (TiCl (CH ₃CH ₂) ₃), triisobutyl titanium chloride (TiCl (i-C ₄H ₉) ₃), three normal-butyl chlorination titanium (TiCl (C ₄H ₉) ₃), dimethyl titanium chloride (TiCl ₂(CH ₃) ₂), diethyl titanium chloride (TiCl ₂(CH ₃CH ₂) ₂), diisobutyl titanium chloride (TiCl ₂(i-C ₄H ₉) ₂), three normal-butyl chlorination titanium (TiCl (C ₄H ₉) ₃), methyl titanium trichloride (Ti (CH ₃) Cl ₃), ethyl titanium trichloride (Ti (CH ₃CH ₂) Cl ₃), isobutyl group titanium trichloride (Ti (i-C ₄H ₉) Cl ₃), normal-butyl titanium trichloride (Ti (C ₄H ₉) Cl ₃);

Trimethyl titanium bromide (TiBr (CH ₃) ₃), triethyl group titanium bromide (TiBr (CH ₃CH ₂) ₃), triisobutyl titanium bromide (TiBr (i-C ₄H ₉) ₃), three normal-butyl bromination titanium (TiBr (C ₄H ₉) ₃), dimethyl dibrominated titanium (TiBr ₂(CH ₃) ₂), diethyl dibrominated titanium (TiBr ₂(CH ₃CH ₂) ₂), diisobutyl dibrominated titanium (TiBr ₂(i-C ₄H ₉) ₂), three normal-butyl bromination titanium (TiBr (C ₄H ₉) ₃), methyl titanium tribromide (Ti (CH ₃) Br ₃), ethyl titanium tribromide (Ti (CH ₃CH ₂) Br ₃), isobutyl group titanium tribromide (Ti (i-C ₄H ₉) Br ₃), normal-butyl titanium tribromide (Ti (C ₄H ₉) Br ₃);

Trimethyl zirconium chloride (ZrCl (CH ₃) ₃), triethyl group zirconium chloride (ZrCl (CH ₃CH ₂) ₃), triisobutyl zirconium chloride (ZrCl (i-C ₄H ₉) ₃), three normal-butyl chlorination zirconium (ZrCl (C ₄H ₉) ₃), dimethyl zirconium dichloride (ZrCl ₂(CH ₃) ₂), diethyl zirconium dichloride (ZrCl ₂(CH ₃CH ₂) ₂), diisobutyl zirconium dichloride (ZrCl ₂(i-C ₄H ₉) ₂), three normal-butyl chlorination zirconium (ZrCl (C ₄H ₉) ₃), methyl tri-chlorination zirconium (Zr (CH ₃) Cl ₃), ethyl tri-chlorination zirconium (Zr (CH ₃CH ₂) Cl ₃), isobutyl group tri-chlorination zirconium (Zr (i-C ₄H ₉) Cl ₃), normal-butyl tri-chlorination zirconium (Zr (C ₄H ₉) Cl ₃);

Trimethyl zirconium bromide (ZrBr (CH ₃) ₃), triethyl group zirconium bromide (ZrBr (CH ₃CH ₂) ₃), triisobutyl zirconium bromide (ZrBr (i-C ₄H ₉) ₃), three normal-butyl bromination zirconium (ZrBr (C ₄H ₉) ₃), dimethyl dibrominated zirconium (ZrBr ₂(CH ₃) ₂), diethyl dibrominated zirconium (ZrBr ₂(CH ₃CH ₂) ₂), diisobutyl dibrominated zirconium (ZrBr ₂(i-C ₄H ₉) ₂), three normal-butyl bromination zirconium (ZrBr (C ₄H ₉) ₃), methyl tribromide zirconium (Zr (CH ₃) Br ₃), ethyl tribromide zirconium (Zr (CH ₃CH ₂) Br ₃), isobutyl group tribromide zirconium (Zr (i-C ₄H ₉) Br ₃), normal-butyl tribromide zirconium (Zr (C ₄H ₉) Br ₃);

Trimethyl hafnium chloride (HfCl (CH ₃) ₃), triethyl group hafnium chloride (HfCl (CH ₃CH ₂) ₃), triisobutyl hafnium chloride (HfCl (i-C ₄H ₉) ₃), three normal-butyl chlorination hafnium (HfCl (C ₄H ₉) ₃), dimethyl hafnium dichloride (HfCl ₂(CH ₃) ₂), diethyl hafnium dichloride (HfCl ₂(CH ₃CH ₂) ₂), diisobutyl hafnium dichloride (HfCl ₂(i-C ₄H ₉) ₂), three normal-butyl chlorination hafnium (HfCl (C ₄H ₉) ₃), methyl tri-chlorination hafnium (Hf (CH ₃) Cl ₃), ethyl tri-chlorination hafnium (Hf (CH ₃CH ₂) Cl ₃), isobutyl group tri-chlorination hafnium (Hf (i-C ₄H ₉) Cl ₃), normal-butyl tri-chlorination hafnium (Hf (C ₄H ₉) Cl ₃);

Trimethyl bromination hafnium (HfBr (CH ₃) ₃), triethyl group bromination hafnium (HfBr (CH ₃CH ₂) ₃), triisobutyl bromination hafnium (HfBr (i-C ₄H ₉) ₃), three normal-butyl bromination hafnium (HfBr (C ₄H ₉) ₃), dimethyl dibrominated hafnium (HfBr ₂(CH ₃) ₂), diethyl dibrominated hafnium (HfBr ₂(CH ₃CH ₂) ₂), diisobutyl dibrominated hafnium (HfBr ₂(i-C ₄H ₉) ₂), three normal-butyl bromination hafnium (HfBr (C ₄H ₉) ₃), methyl tribromide hafnium (Hf (CH ₃) Br ₃), ethyl tribromide hafnium (Hf (CH ₃CH ₂) Br ₃), isobutyl group tribromide hafnium (Hf (i-C ₄H ₉) Br ₃), normal-butyl tribromide hafnium (Hf (C ₄H ₉) Br ₃).

As described IVB family metal alkoxide halide, such as enumerating trimethoxy titanium chloride (TiCl (OCH ₃) ₃), triethoxy titanium chloride (TiCl (OCH ₃CH ₂) ₃), three isobutoxy titanium chloride (TiCl (i-OC ₄H ₉) ₃), three n-butoxy titanium chloride (TiCl (OC ₄H ₉) ₃), dimethoxy titanium chloride (TiCl ₂(OCH ₃) ₂), diethoxy titanium chloride (TiCl ₂(OCH ₃CH ₂) ₂), two isobutoxy titanium chloride (TiCl ₂(i-OC ₄H ₉) ₂), three n-butoxy titanium chloride (TiCl (OC ₄H ₉) ₃), methoxyl group titanium trichloride (Ti (OCH ₃) Cl ₃), ethyoxyl titanium trichloride (Ti (OCH ₃CH ₂) Cl ₃), isobutoxy titanium trichloride (Ti (i-C ₄H ₉) Cl ₃), n-butoxy titanium trichloride (Ti (OC ₄H ₉) Cl ₃);

Trimethoxy titanium bromide (TiBr (OCH ₃) ₃), triethoxy titanium bromide (TiBr (OCH ₃CH ₂) ₃), three isobutoxy titanium bromide (TiBr (i-OC ₄H ₉) ₃), three n-butoxy titanium bromide (TiBr (OC ₄H ₉) ₃), dimethoxy dibrominated titanium (TiBr ₂(OCH ₃) ₂), diethoxy dibrominated titanium (TiBr ₂(OCH ₃CH ₂) ₂), two isobutoxy dibrominated titanium (TiBr ₂(i-OC ₄H ₉) ₂), three n-butoxy titanium bromide (TiBr (OC ₄H ₉) ₃), methoxyl group titanium tribromide (Ti (OCH ₃) Br ₃), ethyoxyl titanium tribromide (Ti (OCH ₃CH ₂) Br ₃), isobutoxy titanium tribromide (Ti (i-C ₄H ₉) Br ₃), n-butoxy titanium tribromide (Ti (OC ₄H ₉) Br ₃);

Trimethoxy zirconium chloride (ZrCl (OCH ₃) ₃), triethoxy zirconium chloride (ZrCl (OCH ₃CH ₂) ₃), three isobutoxy zirconium chloride (ZrCl (i-OC ₄H ₉) ₃), three n-butoxy zirconium chloride (ZrCl (OC ₄H ₉) ₃), dimethoxy zirconium dichloride (ZrCl ₂(OCH ₃) ₂), diethoxy zirconium dichloride (ZrCl ₂(OCH ₃CH ₂) ₂), two isobutoxy zirconium dichloride (ZrCl ₂(i-OC ₄H ₉) ₂), three n-butoxy zirconium chloride (ZrCl (OC ₄H ₉) ₃), methoxyl group tri-chlorination zirconium (Zr (OCH ₃) Cl ₃), ethyoxyl tri-chlorination zirconium (Zr (OCH ₃CH ₂) Cl ₃), isobutoxy tri-chlorination zirconium (Zr (i-C ₄H ₉) Cl ₃), n-butoxy tri-chlorination zirconium (Zr (OC ₄H ₉) Cl ₃);

Trimethoxy zirconium bromide (ZrBr (OCH ₃) ₃), triethoxy zirconium bromide (ZrBr (OCH ₃CH ₂) ₃), three isobutoxy zirconium bromide (ZrBr (i-OC ₄H ₉) ₃), three n-butoxy zirconium bromide (ZrBr (OC ₄H ₉) ₃), dimethoxy dibrominated zirconium (ZrBr ₂(OCH ₃) ₂), diethoxy dibrominated zirconium (ZrBr ₂(OCH ₃CH ₂) ₂), two isobutoxy dibrominated zirconium (ZrBr ₂(i-OC ₄H ₉) ₂), three n-butoxy zirconium bromide (ZrBr (OC ₄H ₉) ₃), methoxyl group tribromide zirconium (Zr (OCH ₃) Br ₃), ethyoxyl tribromide zirconium (Zr (OCH ₃CH ₂) Br ₃), isobutoxy tribromide zirconium (Zr (i-C ₄H ₉) Br ₃), n-butoxy tribromide zirconium (Zr (OC ₄H ₉) Br ₃);

Trimethoxy hafnium chloride (HfCl (OCH ₃) ₃), triethoxy hafnium chloride (HfCl (OCH ₃CH ₂) ₃), three isobutoxy hafnium chloride (HfCl (i-OC ₄H ₉) ₃), three n-butoxy hafnium chloride (HfCl (OC ₄H ₉) ₃), dimethoxy hafnium dichloride (HfCl ₂(OCH ₃) ₂), diethoxy hafnium dichloride (HfCl ₂(OCH ₃CH ₂) ₂), two isobutoxy hafnium dichloride (HfCl ₂(i-OC ₄H ₉) ₂), three n-butoxy hafnium chloride (HfCl (OC ₄H ₉) ₃), methoxyl group tri-chlorination hafnium (Hf (OCH ₃) Cl ₃), ethyoxyl tri-chlorination hafnium (Hf (OCH ₃CH ₂) Cl ₃), isobutoxy tri-chlorination hafnium (Hf (i-C ₄H ₉) Cl ₃), n-butoxy tri-chlorination hafnium (Hf (OC ₄H ₉) Cl ₃);

Trimethoxy bromination hafnium (HfBr (OCH ₃) ₃), triethoxy bromination hafnium (HfBr (OCH ₃CH ₂) ₃), three isobutoxy bromination hafnium (HfBr (i-OC ₄H ₉) ₃), three n-butoxy bromination hafnium (HfBr (OC ₄H ₉) ₃), dimethoxy dibrominated hafnium (HfBr ₂(OCH ₃) ₂), diethoxy dibrominated hafnium (HfBr ₂(OCH ₃CH ₂) ₂), two isobutoxy dibrominated hafnium (HfBr ₂(i-OC ₄H ₉) ₂), three n-butoxy bromination hafnium (HfBr (OC ₄H ₉) ₃), methoxyl group tribromide hafnium (Hf (OCH ₃) Br ₃), ethyoxyl tribromide hafnium (Hf (OCH ₃CH ₂) Br ₃), isobutoxy tribromide hafnium (Hf (i-C ₄H ₉) Br ₃), n-butoxy tribromide hafnium (Hf (OC ₄H ₉) Br ₃).

As described IVB family metallic compound, preferred described IVB family metal halide, more preferably TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄And HfBr ₄, TiCl most preferably ₄And ZrCl ₄

These IVB family metallic compounds can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.

When described chemical treatments is liquid state at normal temperatures, can use described chemical treatments by the mode that in the reaction object (being aforesaid modification carrier) that remains to utilize this chemical treatments to handle, directly drips the described chemical treatments of scheduled volume.

When described chemical treatments when being solid-state at normal temperatures, for measure with easy to operate for the purpose of, preferably use described chemical treatments with the form of solution.Certainly, when described chemical treatments is liquid state at normal temperatures, also can use described chemical treatments as required sometimes, not special the qualification with the form of solution.

When the solution of the described chemical treatments of preparation, to this moment employed solvent there is no particular limitation, as long as it can dissolve this chemical treatments.

Particularly, can enumerate C _5-12Alkane and halo C _5-12Alkane etc., such as enumerating pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, cyclohexane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro hendecane, chlorinated dodecane and chlorocyclohexane etc., wherein preferred pentane, hexane, decane and cyclohexane, most preferably hexane.

These solvents can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.

Clearly, can not select for use this moment and have the solvent (such as ether solvent such as oxolane etc.) of solvability to dissolve described chemical treatments described magnesium compound.

In addition, there is no particular limitation to the concentration of described chemical treatments in its solution, can suitably select as required, as long as it can realize implementing described chemical treatment with the described chemical treatments of scheduled volume.As previously mentioned,, can directly use chemical treatments to carry out described processing, but use after also it can being modulated into the chemical treatment agent solution if chemical treatments is liquid.Be that the molar concentration of described chemical treatments in its solution generally is set at 0.01～1.0mol/L, but is not limited to this easily.

As carrying out described chemically treated method, such as enumerating, under the situation that adopts solid chemical processing agent (such as zirconium chloride), the solution that at first prepares described chemical treatments, the described chemical treatments of adding in pending described modification carrier then (the preferred dropping) scheduled volume; Under the situation that adopts liquid chemical inorganic agent (such as titanium tetrachloride), can be directly (but also can after being prepared into solution) the described chemical treatments of scheduled volume is added in (the preferred dropping) pending described modification carrier, and chemical treatment reaction (in case of necessity by stirring) was carried out 0.5～24 hour, preferred 1～8 hour, more preferably 2～6 hours, filter then, wash and dry getting final product.

According to the present invention, described filtration, washing and drying can adopt conventional method to carry out, and wherein washer solvent can adopt used identical solvent when dissolving described chemical treatments.This washing is generally carried out 1～8 time, and preferred 2～6 times, most preferably 2～4 times.

According to the present invention, consumption as described chemical treatments, make and to reach 1: 0.01-1, preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30 in the described magnesium compound (solid) of Mg element and mol ratio in the described chemical treatments of IVB family metal (such as Ti) element.

Special embodiment according to the present invention, the preparation method of load type non-metallocene catalyst of the present invention also is included in and adopts described chemical treatments to handle before the described modification carrier, with being selected from aikyiaiurnirsoxan beta, alkyl aluminum or its step that helps the described modification carrier of chemical treatments preliminary treatment (pre-treatment step) that makes up arbitrarily.Then, according to carrying out described chemical treatment with described chemical treatments, just described modification carrier is replaced with the pretreated modification carrier of described process and get final product again with aforementioned identical mode.

Below the described chemical treatments that helps is carried out specific description.

According to the present invention, as the described chemical treatments that helps, such as enumerating aikyiaiurnirsoxan beta and alkyl aluminum.

As described aikyiaiurnirsoxan beta, such as enumerating the line style aikyiaiurnirsoxan beta shown in the following general formula (I): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in the following general formula (II) :-(Al (R)-O-) _N+2-.

In aforementioned formula, radicals R is same to each other or different to each other (preferably identical), is selected from C independently of one another ₁-C ₈Alkyl, preferable methyl, ethyl and isobutyl group, most preferable; N is the arbitrary integer in the 1-50 scope, the arbitrary integer in preferred 10～30 scopes.

As described aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide and normal-butyl alumina alkane, further preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.

These aikyiaiurnirsoxan beta can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.

As described alkyl aluminum, such as enumerating the compound shown in the following general formula (III):

Al(R) ₃ (III)

Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from C independently of one another ₁-C ₈Alkyl, preferable methyl, ethyl and isobutyl group, most preferable.

Particularly, as described alkyl aluminum, such as enumerating trimethyl aluminium (Al (CH ₃) ₃), triethyl aluminum (Al (CH ₃CH ₂) ₃), tri-propyl aluminum (Al (C ₃H ₇) ₃), triisobutyl aluminium (Al (i-C ₄H ₉) ₃), three n-butylaluminum (Al (C ₄H ₉) ₃), triisopentyl aluminium (Al (i-C ₅H ₁₁) ₃), three n-pentyl aluminium (Al (C ₅H ₁₁) ₃), three hexyl aluminium (Al (C ₆H ₁₃) ₃), three isohesyl aluminium (Al (i-C ₆H ₁₃) ₃), diethylmethyl aluminium (Al (CH ₃) (CH ₃CH ₂) ₂) and dimethyl ethyl aluminium (Al (CH ₃CH ₂) (CH ₃) ₂) etc., wherein preferred trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.

These alkyl aluminums can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.

According to the present invention, as the described chemical treatments that helps, can only adopt described aikyiaiurnirsoxan beta, also can only adopt described alkyl aluminum, but also can adopt any mixture of described aikyiaiurnirsoxan beta and described alkyl aluminum.And there is no particular limitation to the ratio of each component in this mixture, can select arbitrarily as required.

According to the present invention, the described chemical treatments that helps generally is to use with the form of solution.When the described solution that helps chemical treatments of preparation, to this moment employed solvent there is no particular limitation, as long as it can dissolve this and help chemical treatments.

Particularly, as described solvent, such as enumerating C _5-12Alkane and halo C _5-12Alkane etc., such as enumerating pentane, hexane, heptane, octane, nonane, decane, hendecane, dodecane, cyclohexane, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro hendecane, chlorinated dodecane and chlorocyclohexane etc., wherein preferred pentane, hexane, decane and cyclohexane, most preferably hexane.

Clearly, can not select for use this moment and have the solvent (such as ether solvent such as oxolane etc.) of solvability to dissolve the described chemical treatments that helps described magnesium compound.

These solvents can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.

It in addition, helps the concentration of chemical treatments in its solution there is no particular limitation, can suitably select as required, as long as can realize carrying out described preliminary treatment with the described chemical treatments that helps of scheduled volume to described.

As carrying out described pretreated method, such as enumerating, at first prepare the described solution that helps chemical treatments, then under the temperature of-30～60 ℃ (preferred-20～30 ℃), to intending being metered into (the preferred dropping) described chemical treatment agent solution (the described chemical treatments that helps that contains scheduled volume) that helps with described helping in the pretreated modification carrier of chemical treatments, perhaps add described modification carrier to the described chemical treatment agent solution amount of falling into a trap that helps, form reaction mixture thus, make its reaction 1～8h, preferred 2～6h, most preferably 3～4h (in case of necessity by stirring) gets final product.Then, the preliminary treatment product process that is obtained is filtered, washed (1～6 time, preferred 1～3 time) and optionally drying, and from this reaction mixture, separate, perhaps, also can be and be directly used in follow-up reactions steps with the form of mixed liquor without this separation.At this moment, owing to contained certain amount of solvent in the described mixed liquor, so the solvent load that relates in can the described subsequent reactions step of corresponding minimizing.

According to the present invention,, make to reach 1: 0-1.0, preferred 1: 0-0.5, more preferably 1: 0.1-0.5 in the described magnesium compound (solid) of Mg element and the described mol ratio of chemical treatments that helps in the Al element as the described consumption that helps chemical treatments.

Known to those skilled in the artly be that aforementioned all method step all preferably carries out under the condition of anhydrous anaerobic basically.Here the content that said anhydrous basically anaerobic refers to water and oxygen in the system continues less than 10ppm.And load type non-metallocene catalyst of the present invention needs pressure-fired preservation in confined conditions standby after preparation usually.

According to the present invention, as the consumption of described Nonmetallocene part, make to reach 1: 0.0001-1, preferred 1: 0.0002-0.4 in the described magnesium compound (solid) of Mg element and the mol ratio of described Nonmetallocene part, more preferably 1: 0.0008-0.2, further preferred 1: 0.001-0.1.

According to the present invention, as the consumption of the described solvent that is used to dissolve described magnesium compound, make the described magnesium compound (solid) and the ratio of described solvent reach 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml.

According to the present invention, consumption as described chemical treatments, make and to reach 1: 0.01-1, preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30 in the described magnesium compound (solid) of Mg element and mol ratio in the described chemical treatments of IVB family metal (such as Ti) element.

According to the present invention,, make to reach 1: 0-1.0, preferred 1: 0-0.5, more preferably 1: 0.1-0.5 in the described magnesium compound (solid) of Mg element and the described mol ratio of chemical treatments that helps in the Al element as the described consumption that helps chemical treatments.

According to the present invention,, make that the described precipitating reagent and the volume ratio of the described solvent that is used to dissolve described magnesium compound are 1: 0.2～5, preferred 1: 0.5～2, more preferably 1: 0.8～1.5 as the consumption of described precipitating reagent.

In one embodiment, the invention still further relates to the load type non-metallocene catalyst of making by the preparation method of aforesaid load type non-metallocene catalyst (being also referred to as carry type non-metallocene calalyst for polymerization of olefine sometimes).

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

With regard to this alkene homopolymerization/copolymerization process involved in the present invention, except the following content that particularly points out, other contents of not explaining (such as polymerization with the addition manner of reactor, alkene consumption, catalyst and alkene etc.), can directly be suitable for conventional known those in this area, not special restriction is omitted its explanation at this.

According to homopolymerization/copolymerization process of the present invention, with load type non-metallocene catalyst of the present invention is major catalyst, to be selected from aikyiaiurnirsoxan beta, alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is co-catalyst, makes alkene homopolymerization or copolymerization.

Major catalyst and the co-catalyst adding mode in polymerization reaction system can be to add major catalyst earlier, and then the adding co-catalyst, perhaps add co-catalyst earlier, and then add major catalyst, or add together after both contact mixing earlier, perhaps add simultaneously respectively.Major catalyst and co-catalyst added respectively fashionablely both can in same reinforced pipeline, add successively, also can in the reinforced pipeline of multichannel, add successively, and both add simultaneously respectively and fashionablely should select the multichannel pipeline that feeds in raw material.For the continous way polymerisation, the adding continuously simultaneously of the reinforced pipeline of preferred multichannel, and for the intermittence type polymerization reaction, preferably both mix back adding together in same reinforced pipeline earlier, perhaps in same reinforced pipeline, add co-catalyst earlier, and then add major catalyst.

According to the present invention, there is no particular limitation to the reactive mode of described alkene homopolymerization/copolymerization process, can adopt well known in the art those, such as enumerating 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 described alkene, such as enumerating C ₂～C ₁₀Monoolefine, diolefin, cyclic olefin and other ethylenically unsaturated compounds.

Particularly, as described C ₂～C ₁₀Monoolefine is such as enumerating ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene and styrene etc.; As described cyclic olefin, such as enumerating 1-cyclopentene and ENB etc.; As described diolefin, such as enumerating 1,4-butadiene, 2,5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc.; And as described other ethylenically unsaturated compounds, such as enumerating vinylacetate and (methyl) acrylate etc.Wherein, the homopolymerization of optimal ethylene, the perhaps copolymerization of ethene and propylene, 1-butylene or 1-hexene.

According to the present invention, homopolymerization refers to only a kind of polymerization of described alkene, and copolymerization refers to the polymerization between the two or more described alkene.

According to the present invention, described co-catalyst is selected from aikyiaiurnirsoxan beta, alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, wherein preferred aikyiaiurnirsoxan beta and alkyl aluminum.

As described aikyiaiurnirsoxan beta, such as enumerating the line style aikyiaiurnirsoxan beta shown in the following general formula (I-1): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in the following general formula (II-1) :-(Al (R)-O-) _N+2-.

In aforementioned formula, radicals R is same to each other or different to each other (preferably identical), is selected from C independently of one another ₁-C ₈Alkyl, preferable methyl, ethyl and isobutyl group, most preferable; N is the arbitrary integer in the 1-50 scope, the arbitrary integer in preferred 10～30 scopes.

As described aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide and normal-butyl alumina alkane, further preferable methyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide, and most preferable aikyiaiurnirsoxan beta.

These aikyiaiurnirsoxan beta can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.

As described alkyl aluminum, such as enumerating the compound shown in the following general formula (III-1):

Al(R) ₃ (III-1)

Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from C independently of one another ₁-C ₈Alkyl, preferable methyl, ethyl and isobutyl group, most preferable.

Particularly, as described alkyl aluminum, such as enumerating trimethyl aluminium (Al (CH ₃) ₃), triethyl aluminum (Al (CH ₃CH ₂) ₃), tri-propyl aluminum (Al (C ₃H ₇) ₃), triisobutyl aluminium (Al (i-C ₄H ₉) ₃), three n-butylaluminum (Al (C ₄H ₉) ₃), triisopentyl aluminium (Al (i-C ₅H ₁₁) ₃), three n-pentyl aluminium (Al (C ₅H ₁₁) ₃), three hexyl aluminium (Al (C ₆H ₁₃) ₃), three isohesyl aluminium (Al (i-C ₆H ₁₃) ₃), diethylmethyl aluminium (Al (CH ₃) (CH ₃CH ₂) ₂) and dimethyl ethyl aluminium (Al (CH ₃CH ₂) (CH ₃) ₂) etc., wherein preferred trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, further preferred triethyl aluminum and triisobutyl aluminium, and triethyl aluminum most preferably.

These alkyl aluminums can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.

As described haloalkyl aluminium, described boron fluothane, described boron alkyl and described boron alkyl ammonium salt, can directly use conventional those that use in this area, not special restriction.

In addition, according to the present invention, described co-catalyst can be used alone, and also can be as required be used in combination multiple aforesaid co-catalyst, not special restriction with ratio arbitrarily.

According to the present invention, the difference according to the reactive mode of described alkene homopolymerization/copolymerization process needs to use the polymerization solvent sometimes.

As described polymerization solvent, can use this area conventional those that use when carrying out alkene homopolymerization/copolymerization, not special restriction.

As described polymerization solvent, such as enumerating C _4-10Alkane (such as butane, pentane, hexane, heptane, octane, nonane or decane etc.), halo C _1-10Alkane (such as carrene), aromatic hydrocarbon solvent (such as toluene and dimethylbenzene), ether solvent (such as ether or oxolane), esters solvent (such as ethyl acetate) and ketones solvent (such as acetone) etc.Wherein, preferably use hexane as described polymerization solvent.

These polymerizations can be used alone with solvent, perhaps are used in combination multiple with ratio arbitrarily.

According to the present invention, the polymerization pressure of described alkene homopolymerization/copolymerization process is generally 0.1～10MPa, preferred 0.1～4MPa, and more preferably 1～3MPa, but be not limited to this sometimes.According to the present invention, polymeric reaction temperature is generally-40 ℃～200 ℃, and preferred 10 ℃～100 ℃, more preferably 40 ℃～90 ℃, but be not limited to this sometimes.

In addition, according to the present invention, described alkene homopolymerization/copolymerization process can carry out under the condition that has hydrogen to exist, and also can carry out under the condition that does not have hydrogen to exist.Under situation about existing, the dividing potential drop of hydrogen can be 0.01%～99% of a described polymerization pressure, and is preferred 0.01%～50%, but is not limited to this sometimes.

According to the present invention, when carrying out described alkene homopolymerization/copolymerization process, be generally 1: 1～1000 in the described co-catalyst of aluminium or boron and mol ratio in the described load type non-metallocene catalyst of IVB family metal, preferred 1: 1～500, more preferably 1: 10～500, but be not limited to this sometimes.

Embodiment

Below adopt embodiment that the present invention is described in further detail, but the present invention is not limited to these embodiment.

(unit is g/cm to polymer stacks density ³) mensuration carry out with reference to CNS GB1636-79.

The content of IVB family metal (such as Ti) and Mg element adopts the ICP-AES method to measure in the load type non-metallocene catalyst, and the content of Nonmetallocene part adopts analyses.

The polymerization activity of catalyst calculates in accordance with the following methods: after polymerisation finishes, polymerizate in the reactor is filtered and drying, the quality of this polymerizate of weighing then represents that divided by the ratio of the quality of used load type non-metallocene catalyst (unit is kg polymer/g catalyst or kg polymer/gCat) for the polymerization activity of this catalyst with this polymerizate quality.

Molecular weight Mw, the Mn of polymer and molecular weight distribution (Mw/Mn) adopt the GPC V2000 type gel chromatography analyzer of U.S. WATERS company to measure, and are solvent with adjacent trichloro-benzenes, and the temperature during mensuration is 150 ℃.

The viscosity average molecular weigh of polymer is calculated in accordance with the following methods: according to standard A STMD4020-00, (capillary inner diameter is 0.44mm to adopt high temperature dilution type Ubbelohde viscometer method, the constant temperature bath medium is No. 300 silicone oil, dilution is a decahydronaphthalene with solvent, measuring temperature is 135 ℃) measure the inherent viscosity of described polymer, calculate the viscosity average molecular weigh Mv of described polymer then according to following formula.

Mv＝5.37×10 ⁴×[η] ^1.37

Wherein, η is an inherent viscosity.

Embodiment 1

Magnesium compound adopts anhydrous magnesium chloride, and the solvent of dissolved magnesium compound and Nonmetallocene part adopts oxolane, and chemical treatments adopts titanium tetrachloride.The Nonmetallocene part adopts structure to be

Compound.

Take by weighing 5g anhydrous magnesium chloride and Nonmetallocene part, dissolving fully under the normal temperature behind the adding tetrahydrofuran solvent, stir after 2 hours, add the precipitating reagent hexane and make it precipitation, filter, wash 2 times, each precipitating reagent consumption is with addition is identical before, evenly be heated under 60 ℃ and vacuumize drying, obtain modifying carrier.

Then in described modification carrier, add the 60ml hexane, under stirring condition with 30 minutes dropping titanium tetrachlorides, 60 ℃ of following stirring reactions 4 hours, filter, hexane wash 2 times, each hexane consumption 60ml, vacuum drying obtains load type non-metallocene catalyst under the normal temperature.

Wherein proportioning is, magnesium chloride and oxolane proportioning are 1mol: 210ml; Magnesium chloride and Nonmetallocene part mol ratio are 1: 0.08; Precipitating reagent and oxolane volume proportion are 1: 1; Magnesium chloride and titanium tetrachloride mol ratio are 1: 0.15.

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

Embodiment 1-1

Substantially the same manner as Example 1, but following change is arranged:

The Nonmetallocene part adopts

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into toluene, and precipitating reagent is changed into cyclohexane, and chemical treatments is changed into zirconium chloride (ZrCl ₄).

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 250ml; Magnesium compound and Nonmetallocene part mol ratio are 1: 0.15; The solvent volume proportioning of precipitating reagent and dissolved magnesium compound and Nonmetallocene part is 1: 2; Magnesium compound and chemical treatments mol ratio are 1: 0.20.

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

Embodiment 1-2

Substantially the same manner as Example 1, but following change is arranged:

Magnesium compound is changed into anhydrous magnesium bromide (MgBr ₂), the Nonmetallocene part adopts

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into ethylbenzene, and precipitating reagent is changed into cycloheptane, and chemical treatments is changed into titanium tetrabromide (TiBr ₄).

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 300ml; Magnesium compound and Nonmetallocene part mol ratio are 1: 0.20; The solvent volume proportioning of precipitating reagent and dissolved magnesium compound and Nonmetallocene part is 1: 0.7; Magnesium compound and chemical treatments mol ratio are 1: 0.30.

Load type non-metallocene catalyst is designated as CAT-1-2.

Embodiment 1-3

Substantially the same manner as Example 1, but following change is arranged:

Magnesium compound is changed into ethyoxyl magnesium chloride (MgCl (OC ₂H ₅)), the Nonmetallocene part adopts

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into dimethylbenzene, and precipitating reagent is changed into decane, and chemical treatments adopts tetraethyl titanium (Ti (CH ₃CH ₂) ₄).

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 300ml; Magnesium compound and Nonmetallocene part mol ratio are 1: 0.04; The solvent volume proportioning of precipitating reagent and dissolved magnesium compound and Nonmetallocene part is 1: 1.5; Magnesium compound and chemical treatments mol ratio are 1: 0.05.

Load type non-metallocene catalyst is designated as CAT-1-3.

Embodiment 1-4

Substantially the same manner as Example 1, but following change is arranged:

Magnesium compound is changed into butoxy magnesium bromide (MgBr (OC ₄H ₉)), the Nonmetallocene part adopts The solvent of dissolved magnesium compound and Nonmetallocene part is changed into and ethylbenzene, and chemical treatments adopts tetra-n-butyl titanium (Ti (C ₄H ₉) ₄).

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 400ml; Magnesium compound and Nonmetallocene part mol ratio are 1: 0.30; Magnesium compound and chemical treatments mol ratio are 1: 0.50.

Load type non-metallocene catalyst is designated as CAT-1-4.

Embodiment 1-5

Substantially the same manner as Example 1, but following change is arranged:

Magnesium compound is changed into methyl-magnesium-chloride (Mg (CH ₃) Cl), the Nonmetallocene part adopts

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into chlorotoluene, and chemical treatments adopts tetraethyl zirconium (Zr (CH ₃CH ₂) ₄).

Wherein proportioning is, magnesium compound and Nonmetallocene part mol ratio are 1: 0.10; Magnesium compound and chemical treatments mol ratio are 1: 0.10.

Load type non-metallocene catalyst is designated as CAT-1-5.

Embodiment 1-6

Substantially the same manner as Example 1, but following change is arranged:

Magnesium compound is changed into ethylmagnesium chloride (Mg (C ₂H ₅) Cl), the Nonmetallocene part adopts

Chemical treatments adopts purity titanium tetraethoxide (Ti (OCH ₃CH ₂) ₄).

Load type non-metallocene catalyst is designated as CAT-1-6.

Embodiment 1-7

Substantially the same manner as Example 1, but following change is arranged:

Magnesium compound is changed into magnesium ethide (Mg (C ₂H ₅) ₂), the Nonmetallocene part adopts

Chemical treatments adopts isobutyl group titanium trichloride (Ti (i-C ₄H ₉) Cl ₃).

Load type non-metallocene catalyst is designated as CAT-1-7.

Embodiment 1-8

Substantially the same manner as Example 1, but following change is arranged:

Magnesium compound is changed into methyl ethoxy magnesium (Mg (OC ₂H ₅) (CH ₃)), chemical treatments is changed into three isobutoxy titanium chloride (TiCl (i-OC ₄H ₉) ₃).

Load type non-metallocene catalyst is designated as CAT-1-8.

Embodiment 1-9

Substantially the same manner as Example 1, but following change is arranged:

Magnesium compound is changed into ethyl n-butoxy magnesium (Mg (OC ₄H ₉) (C ₂H ₅)), chemical treatments is changed into dimethoxy zirconium dichloride (ZrCl ₂(OCH ₃) ₂).

Load type non-metallocene catalyst is designated as CAT-1-9.

Embodiment 2

Magnesium compound adopts anhydrous magnesium chloride, and the solvent of dissolved magnesium compound and Nonmetallocene part adopts oxolane, and chemical treatments adopts titanium tetrachloride.The Nonmetallocene part adopts structure to be Compound.

Take by weighing 5g anhydrous magnesium chloride and Nonmetallocene part, dissolving fully under the normal temperature behind the adding tetrahydrofuran solvent, stir after 2 hours, add the precipitating reagent hexane and make it precipitation, filter, wash 2 times, each precipitating reagent consumption is with addition is identical before, evenly be heated under 60 ℃ and vacuumize drying, obtain modifying carrier.

Then in the modification carrier that is obtained, add the 60ml hexane, under stirring condition, adopt triethyl aluminum (concentration is the hexane solution of 15wt%) to help chemical treatments to handle complex carrier, with 30 minutes dropping triethyl aluminums, 60 ℃ of following stirring reactions are after 4 hours, filter, hexane wash 2 times, each hexane consumption 60ml, vacuum drying obtains preliminary treatment and modifies carrier under the normal temperature.

Modify in the carrier to described preliminary treatment then and add the 60ml hexane again, under stirring condition with 30 minutes dropping titanium tetrachlorides, 60 ℃ of following stirring reactions 4 hours, filter, hexane wash 2 times, each hexane consumption 60ml, vacuum drying obtains load type non-metallocene catalyst under the normal temperature.

Wherein proportioning is, magnesium chloride and oxolane proportioning are 1mol: 210ml; Magnesium chloride and Nonmetallocene part mol ratio are 1: 0.08; Precipitating reagent and oxolane volume proportion are 1: 1; Magnesium chloride and triethyl aluminum mol ratio are 1: 0.15; Magnesium chloride and titanium tetrachloride mol ratio are 1: 0.15.

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

Embodiment 2-1

Substantially the same manner as Example 2, but following change is arranged:

The Nonmetallocene part adopts

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into toluene, and precipitating reagent is changed into cyclohexane, helps chemical treatments to change into MAO (MAO, the toluene solution of 10wt%), and chemical treatments is changed into zirconium chloride (ZrCl ₄).

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 250ml; Magnesium compound and Nonmetallocene part mol ratio are 1: 0.15; The solvent volume proportioning of precipitating reagent and dissolved magnesium compound and Nonmetallocene part is 1: 2; Magnesium compound is 1: 0.15 with helping the chemical treatments mol ratio; Magnesium compound and chemical treatments mol ratio are 1: 0.20.

Load type non-metallocene catalyst is designated as CAT-2-1.

Embodiment 2-2

Substantially the same manner as Example 2, but following change is arranged:

Magnesium compound is changed into anhydrous magnesium bromide (MgBr ₂), the Nonmetallocene part adopts

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into ethylbenzene, and precipitating reagent is changed into cycloheptane, and chemical treatments is changed into titanium tetrabromide (TiBr ₄), chemical treatments is changed into titanium tetrabromide (TiBr ₄).

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 300ml; Magnesium compound and Nonmetallocene part mol ratio are 1: 0.20; The solvent volume proportioning of precipitating reagent and dissolved magnesium compound and Nonmetallocene part is 1: 0.7; Magnesium compound is 1: 0.30 with helping the chemical treatments mol ratio; Magnesium compound and chemical treatments mol ratio are 1: 0.30.

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

Embodiment 2-3

Substantially the same manner as Example 2, but following change is arranged:

Magnesium compound is changed into ethyoxyl magnesium chloride (MgCl (OC ₂H ₅)), the Nonmetallocene part adopts The solvent of dissolved magnesium compound and Nonmetallocene part is changed into dimethylbenzene, and precipitating reagent is changed into decane, helps chemical treatments to change into triisobutyl aluminium (Al (i-C ₄H ₉) ₃), chemical treatments adopts tetraethyl titanium (Ti (CH ₃CH ₂) ₄).

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 300ml; Magnesium compound and Nonmetallocene part mol ratio are 1: 0.04; The solvent volume proportioning of precipitating reagent and dissolved magnesium compound and Nonmetallocene part is 1: 1.5; Magnesium compound is 1: 0.05 with helping the chemical treatments mol ratio; Magnesium compound and chemical treatments mol ratio are 1: 0.05.

Load type non-metallocene catalyst is designated as CAT-2-3.

Embodiment 2-4

Substantially the same manner as Example 2, but following change is arranged:

Magnesium compound is changed into butoxy magnesium bromide (MgBr (OC ₄H ₉)), the Nonmetallocene part adopts

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into and ethylbenzene, helps chemical treatments to change into isobutyl aluminium alkoxide, and chemical treatments adopts tetra-n-butyl titanium (Ti (C ₄H ₉) ₄).

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 400ml; Magnesium compound and Nonmetallocene part mol ratio are 1: 0.30; Magnesium compound is 1: 0.50 with helping the chemical treatments mol ratio; Magnesium compound and chemical treatments mol ratio are 1: 0.50.

Load type non-metallocene catalyst is designated as CAT-2-4.

Embodiment 2-5

Substantially the same manner as Example 1, but following change is arranged:

Magnesium compound is changed into methyl-magnesium-chloride (Mg (CH ₃) Cl), the Nonmetallocene part adopts

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into chlorotoluene, helps chemical treatments to change into diethylmethyl aluminium (Al (CH ₃) (CH ₃CH ₂) ₂), chemical treatments adopts tetraethyl zirconium (Zr (CH ₃CH ₂) ₄).

Wherein proportioning is, magnesium compound and Nonmetallocene part mol ratio are 1: 0.10; Magnesium compound is 1: 0.10 with helping the chemical treatments mol ratio; Magnesium compound and chemical treatments mol ratio are 1: 0.10.

Load type non-metallocene catalyst is designated as CAT-2-5.

The comparative example A

Substantially the same manner as Example 1, but following change is arranged:

Do not add the Nonmetallocene part.

Catalyst is designated as CAT-A.

Comparative Examples B

Substantially the same manner as Example 1, but following change is arranged:

It is 1: 0.16 that magnesium chloride and Nonmetallocene part mol ratio are changed into;

Catalyst is designated as CAT-B.

Comparative Examples C

Substantially the same manner as Example 1, but following change is arranged:

It is 1: 0.04 that magnesium chloride and Nonmetallocene part mol ratio are changed into;

Catalyst is designated as CAT-C.

Comparative Examples D

Substantially the same manner as Example 1, but following change is arranged:

Modifying carrier handles without titanium tetrachloride.

Catalyst is designated as CAT-D.

Application Example

With catalyst CAT-1～CAT-2, CAT-1-1～5 that make in the embodiment of the invention, CAT-2-1～5, CAT-A～D, carry out homopolymerization, copolymerization and the preparation ultra-high molecular weight polyethylene of ethene under the following conditions in accordance with the following methods respectively.

Homopolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction time.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, add 50mg load type non-metallocene catalyst and catalyst mixture then, add hydrogen again, continue to feed ethene at last and make the polymerization stagnation pressure constant at 0.8MPa to 0.2MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry back weighing quality.The concrete condition of this polymerisation and polymerization evaluation result are as shown in table 1.

Copolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction time.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, add 50mg load type non-metallocene catalyst and catalyst mixture then, disposable adding hexene-1 comonomer 50g, add hydrogen again to 0.2MPa, continue to feed ethene at last and make the polymerization stagnation pressure constant at 0.8MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry back weighing quality.The concrete condition of this polymerisation and polymerization evaluation result are as shown in table 1.

The preparation ultra-high molecular weight polyethylene is polymerized to: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.5MPa, 70 ℃ of polymerization temperatures, 6 hours reaction time.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, add 50mg load type non-metallocene catalyst and catalyst mixture then, co-catalyst and reactive metal mol ratio are 100, continue to feed ethene at last and make the polymerization stagnation pressure constant in 0.5MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry back weighing quality.The concrete condition of this polymerisation and polymerization evaluation result are as shown in table 2.

Result of the test data by sequence number 12 in sequence number in the table 13 and 4, the table 2 and 13 increase the consumption of co-catalyst as can be known, promptly improve co-catalyst and catalyst activity metal molar than the time, influence active to polymerization catalyst and polymer stacks density is not remarkable.It can be said that brightly, adopt the load type non-metallocene catalyst of method provided by the invention preparation only to need fewer co-catalyst consumption just can obtain high olefin polymerizating activity; And polymer such as resulting polyethylene has good polymer morphology and high polymer bulk density thus.

Sequence number 1 and 3 in the contrast table 1, sequence number 10 and 12 result of the test data are as can be known, after the copolymerization, catalyst activity has greatly to be increased, thereby explanation adopts the load type non-metallocene catalyst of method preparation provided by the invention to have comparatively significant comonomer effect.

Result of the test data by sequence number 1 in the contrast table 1 and Comparative Examples sequence number 19～21 reduce or increase the addition of Nonmetallocene part as can be known in the catalyst, its activity decreases or increases, and the molecular weight distribution of polymer also broadens thereupon or narrows down.Reduce in the catalyst or the increase chemical treatments, its activity decreases or increases, and the molecular weight distribution of polymer also narrows down thereupon or broadens.Thereby illustrate that the Nonmetallocene part has the effect of the molecular weight distribution of narrowing, and chemical treatments has the effect that improves catalyst activity and broadening molecular weight distribution.Therefore the researcher in this field knows, can obtain the catalyst of different activities and polymer performance by the proportioning that changes both.

By the data of sequence number 8 in sequence number in the table 1 22 and the table 2 as can be known, catalyst contains the Nonmetallocene part does not merely have polymerization activity, must with just have polymerization activity after the IVB compounds of group combines.

Sequence number 1-9 and 10-18 in the contrast table 1, sequence number 1-2 and 3-4 are as seen in the table 2, modify carrier with handling with co-catalyst earlier, and then handle resulting load type non-metallocene catalyst with chemical treatments, with only handle resulting load type non-metallocene catalyst and compare with chemical treatments, catalytic activity and polymer stacks density are higher, and molecular weight distribution is narrower, and the ultra-high molecular weight polyethylene viscosity average molecular weigh is higher.

By the data of sequence number 6 in sequence number in the table 1 13 and the table 2 as can be known, catalyst contains the Nonmetallocene part does not merely have polymerization activity, must with just have polymerization activity after the IVB compounds of group combines.

By table 2 as seen, adopt catalyst provided by the present invention, can prepare ultra-high molecular weight polyethylene, its bulk density all increases to some extent, and contrast sequence number 1 and 2,3 and 4 as seen, adopts MAO can increase the viscosity average molecular weigh of polymer as co-catalyst.The result of the test data of sequence number 1 and Comparative Examples 5-7 reduce in the catalyst or increase Nonmetallocene part as can be known in the contrast table 2, and the polymer viscosity average molecular weigh reduces thereupon or increases.Thereby the effect that the Nonmetallocene part also has increases the polymer viscosity average molecular weigh is described.

Though more than in conjunction with the embodiments the specific embodiment of the present invention is had been described in detail, it is pointed out that protection scope of the present invention is not subjected to the restriction of these specific embodiment, but determine by claims of appendix.Those skilled in the art can carry out suitable change to these embodiments in the scope that does not break away from technological thought of the present invention and purport, and these embodiments after changing obviously are also included within protection scope of the present invention.

Claims (13)

1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:

Magnesium compound and Nonmetallocene part are dissolved in the solvent, obtain the step of magnesium compound solution;

In described magnesium compound solution, add precipitating reagent, obtain to modify the step of carrier; With

Handle described modification carrier with the chemical treatments that is selected from IVB family metallic compound, obtain the step of described load type non-metallocene catalyst.

2. according to the described preparation method of claim 1, also be included in and adopt described chemical treatments to handle before the described modification carrier, with being selected from aikyiaiurnirsoxan beta, alkyl aluminum or its step that helps the described modification carrier of chemical treatments preliminary treatment that makes up arbitrarily.

3. according to the described preparation method of claim 1, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide, alkoxyl magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and the alkyl alkoxy magnesium, is preferably selected from the magnesium halide one or more, more preferably magnesium chloride.

4. according to the described preparation method of claim 1, it is characterized in that described solvent is selected from C _6-12Aromatic hydrocarbon, halo C _6-12In aromatic hydrocarbon, ester and the ether one or more are preferably selected from C _6-12In aromatic hydrocarbon and the oxolane one or more, most preferably oxolane.

5. according to the described preparation method of claim 1, it is characterized in that described Nonmetallocene part is selected from one or more in the compound with following chemical structural formula:

Be preferably selected from compound (A) with following chemical structural formula and in the compound (B) one or more:

More preferably be selected to compound (A-4) and compound (B-1) to compound (B-4) one or more of compound (A-1) with following chemical structural formula:

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

A be selected from oxygen atom, sulphur atom, selenium atom,

-NR ²³R ²⁴,-N (O) R ²⁵R ²⁶,

-PR ²⁸R ²⁹,-P (O) R ³⁰OR ³¹, sulfuryl, sulfoxide group or-Se (O) R ³⁹, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C ₁-C ₃₀Alkyl;

D is selected from nitrogen-atoms, oxygen atom, sulphur atom, selenium atom, phosphorus atoms, nitrogen-containing group, phosphorus-containing groups, C ₁-C ₃₀Alkyl, sulfuryl, sulfoxide group,

-N (O) R ²⁵R ²⁶, Or-P (O) R ³²(OR ³³), N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

G is selected from C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group;

Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contain seleno group or phosphorus-containing groups, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

→ represent singly-bound or two key;

-represent covalent bond or ionic bond;

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from hydrogen, C independently of one another ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, is preferably formed aromatic ring; And

R ⁵Be selected from lone pair electrons on the nitrogen, hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R ⁵For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R ⁵In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family metallic atom,

Described Nonmetallocene part further is preferably selected from one or more in the compound with following chemical structural formula:

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

6. according to the described preparation method of claim 5, it is characterized in that,

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

Described nitrogen-containing group is selected from -NR ²³R ²⁴,-T-NR ²³R ²⁴Or-N (O) R ²⁵R ²⁶

Described phosphorus-containing groups is selected from -PR ²⁸R ²⁹,-P (O) R ³⁰R ³¹Or-P (O) R ³²(OR ³³);

Described oxy radical be selected from hydroxyl ,-OR ³⁴With-T-OR ³⁴

Described sulfur-containing group is selected from-SR ³⁵,-T-SR ³⁵,-S (O) R ³⁶Or-T-SO ₂R ³⁷

The described seleno group that contains is selected from-SeR ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹Or-T-Se (O) R ³⁹

Described group T is selected from C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group;

Described R ³⁷Be selected from hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group;

Described C ₁-C ₃₀Alkyl is selected from C ₁-C ₃₀Alkyl, C ₇-C ₅₀Alkaryl, C ₇-C ₅₀Aralkyl, C ₃-C ₃₀Cyclic alkyl, C ₂-C ₃₀Thiazolinyl, C ₂-C ₃₀Alkynyl, C ₆-C ₃₀Aryl, C ₈-C ₃₀Condensed ring radical or C ₄-C ₃₀Heterocyclic radical, wherein said heterocyclic radical contain 1-3 hetero atom that is selected from nitrogen-atoms, oxygen atom or sulphur atom;

The C of described replacement ₁-C ₃₀Alkyl is selected from and has one or more aforementioned halogens or aforementioned C ₁-C ₃₀Alkyl is as substituent aforementioned C ₁-C ₃₀Alkyl;

Described safing function group is selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, contains tin group, C ₁-C ₁₀Ester group and nitro,

Wherein, described silicon-containing group is selected from-SiR ⁴²R ⁴³R ⁴⁴Or-T-SiR ⁴⁵Described germanic group is selected from-GeR ⁴⁶R ⁴⁷R ⁴⁸Or-T-GeR ⁴⁹Describedly contain tin group and be selected from-SnR ⁵⁰R ⁵¹R ⁵²,-T-SnR ⁵³Or-T-Sn (O) R ⁵⁴And described R ⁴²To R ⁵⁴Be selected from hydrogen, aforementioned C independently of one another ₁-C ₃₀The C of alkyl, aforementioned replacement ₁-C ₃₀Alkyl or aforementioned safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and described group T ditto defines.

7. according to the described preparation method of claim 1, it is characterized in that, in the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene part is 1: 0.0001-1, preferred 1: 0.0002-0.4, more preferably 1: 0.0008-0.2, further preferred 1: 0.001-0.1, the ratio of described magnesium compound and described solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml, the volume ratio of described precipitating reagent and described solvent is 1: 0.2～5, preferred 1: 0.5～2, more preferably 1: 0.8～1.5, and be 1 in the described magnesium compound of Mg element with mol ratio in the described chemical treatments of IVB family metallic element: 0.01-1, preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30.

8. according to the described preparation method of claim 1, it is characterized in that, described precipitating reagent is selected from alkane, cycloalkane, in halogenated alkane and the halo cycloalkane one or more, be preferably selected from pentane, hexane, heptane, octane, nonane, decane, cyclohexane, pentamethylene, cycloheptane, cyclodecane, cyclononane, carrene, dichloro hexane, two chloroheptanes, chloroform, trichloroethanes, three chlorobutanes, methylene bromide, Bromofume, dibromo-heptane, bromoform, tribromoethane, three NBBs, chlorocyclopentane, chlorocyclohexane, the chloro cycloheptane, the chloro cyclooctane, the chloro cyclononane, the chloro cyclodecane, bromocyclopentane, bromocyclohexane, the bromo cycloheptane, the bromo cyclooctane, in bromo cyclononane and the bromo cyclodecane one or more, further be preferably selected from hexane, heptane, in decane and the cyclohexane one or more, most preferably hexane.

9. according to the described preparation method of claim 1, it is characterized in that, described IVB family metallic compound is selected from one or more in IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, IVB family metal alkyl halides and the IVB family metal alkoxide halide, be preferably selected from the IVB family metal halide one or more, more preferably be selected from TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄And HfBr ₄In one or more, most preferably be selected from TiCl ₄And ZrCl ₄In one or more.

10. according to the described preparation method of claim 2, it is characterized in that, described aikyiaiurnirsoxan beta is selected from MAO, the ethyl aikyiaiurnirsoxan beta, in isobutyl aluminium alkoxide and the normal-butyl alumina alkane one or more, more preferably be selected from MAO and the isobutyl aluminium alkoxide one or more, and described alkyl aluminum is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminium, three n-pentyl aluminium, three hexyl aluminium, three isohesyl aluminium, in diethylmethyl aluminium and the dimethyl ethyl aluminium one or more, be preferably selected from trimethyl aluminium, triethyl aluminum, in tri-propyl aluminum and the triisobutyl aluminium one or more most preferably are selected from triethyl aluminum and the triisobutyl aluminium one or more.

It 11., it is characterized in that, is 1 with helping the mol ratio of chemical treatments: 0-1.0, preferred 1: 0-0.5, more preferably 1: 0.1-0.5 in Al element described in the described magnesium compound of Mg element according to the described preparation method of claim 2.

12. a load type non-metallocene catalyst, it is by making according to each described preparation method of claim 1-11.

13. alkene homopolymerization/copolymerization process, it is characterized in that, being major catalyst according to the described load type non-metallocene catalyst of claim 12, to be selected from aikyiaiurnirsoxan beta, alkyl aluminum, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is co-catalyst, makes alkene homopolymerization or copolymerization.