CN102039190A

CN102039190A - Supported non-metallocene catalyst, preparation method and application thereof

Info

Publication number: CN102039190A
Application number: CN2009101806067A
Authority: CN
Inventors: 李传峰; 任鸿平; 姚小利; 马忠林; 郭峰; 汪开秀; 刘经伟; 王亚明; 杨立娟
Original assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Priority date: 2009-10-26
Filing date: 2009-10-26
Publication date: 2011-05-04
Anticipated expiration: 2029-10-26
Also published as: CN102039190B

Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method thereof. The supported non-metallocene catalyst has the characteristics of simple and feasible preparation method, flexible and adjustable polymerization activity and the like. The invention also relates to application of the supported non-metallocene catalyst in homopolymerization/ copolymerization of olefins. Compared with the prior art, the consumption of a cocatalyst is low in the application.

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 02151294.9 ZL 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 etc. provide multiple mode to carry out load to obtain load type non-metallocene catalyst, but these patents all relate on the carrier after the Nonmetallocene organic compound that will contain transition metal is carried on processing, and catalyst preparation process is comparatively complicated.

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 compound that will contain transition metal is carried on processing.

The catalyst that with the anhydrous magnesium chloride is carrier demonstrates advantages of high catalytic activity in olefin polymerization process, but this type of catalyst is highly brittle, and is broken easily in polymer reactor, thereby causes polymer morphology bad.Silicon dioxide carried catalyst has good flowability, can be used for gas fluidised bed polymerisation, but silicon dioxide carried metallocene and non cyclopentadienyl catalyst then show lower catalytic activity.Therefore, just may prepare and have high catalytic activity, the catalyst of the controlled and good abrasion strength resistance of granule size if magnesium chloride and silica are well organically combined.

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 salicylic alidehyde imine derivative of the salicylic alidehyde imine 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.

Even so, the ubiquitous problem of the load type non-metallocene catalyst that exists in the prior art is, load process complexity, generally need carry out the multistep of carrier and handle afterwards load non-metallocene metal complex again, olefin polymerizating activity is low and be difficult to regulate, and, when carrying out olefinic polymerization, must assist higher co-catalyst consumption in order to improve its polymerization activity.And because the Nonmetallocene complex is carried on the carrier after the processing, it still exists problems such as stability.

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 complex are dissolved in the solvent, obtain the step of magnesium compound solution;

Optional porous carrier through thermal activation treatment is mixed with described magnesium compound solution, obtain the step of mixed serum; With

In described mixed serum, add precipitating reagent, obtain the step of described load type non-metallocene catalyst.

2. according to each described preparation method of aforementioned aspect, it is characterized in that, described porous carrier is selected from olefin homo or copolymer, polyvinyl alcohol or its copolymer, cyclodextrin, polyester or copolyesters, polyamide or copolyamide, ryuron or copolymer, Voncoat R 3310 or copolymer, methacrylic acid ester homopolymer or copolymer, styrene homopolymers or copolymer, the partial cross-linked form of these homopolymers or copolymer, period of element Table II A, III A, the refractory oxides or the infusibility composite oxides of IV A or IV B family metal, clay, molecular sieve, mica, imvite, in bentonite and the diatomite one or more, be preferably selected from partial cross-linked styrene polymer, silica, aluminium oxide, magnesia, the oxidation sial, the oxidation magnalium, titanium dioxide, in molecular sieve and the imvite one or more more preferably are selected from silica.

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 complex 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;

M is 1,2 or 3;

M is selected from periodic table of elements III-th family to XI family metallic atom, preferred IV B family metallic atom, more preferably Ti (IV) and Zr (IV);

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

X is selected from halogen, hydrogen atom, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl, oxy radical, nitrogen-containing group, sulfur-containing group, boron-containing group, contain aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or contain tin group, a plurality of X can be identical, also can be different, and can also be each other in key or Cheng Huan;

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 oxygen atom, 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;

---represent coordinate bond, 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 IV B family metallic atom,

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

Most preferably be selected from the compound with following chemical structural formula one or more:

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 ₁₀Ester group or nitro,

Wherein, described boron-containing group is selected from BF ₄ ^-, (C ₆F ₅) ₄B ^-Or (R ⁴⁰BAr ₃) ^-

Describedly contain aluminium base group and be selected from alkyl aluminum, AlPh ₄ ^-, AlF ₄ ^-, AlCl ₄ ^-, AlBr ₄ ^-, AlI ₄ ^-Or R ⁴¹AlAr ₃ ^-

Described silicon-containing group is selected from-SiR ⁴²R ⁴³R ⁴⁴Or-T-SiR ⁴⁵

Described germanic group is selected from-GeR ⁴⁶R ⁴⁷R ⁴⁸Or-T-GeR ⁴⁹

Describedly contain tin group and be selected from-SnR ⁵⁰R ⁵¹R ⁵²,-T-SnR ⁵³Or-T-Sn (O) R ⁵⁴,

Described Ar represents C ₆-C ₃₀Aryl, and

R ⁴⁰To 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, wherein these groups 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 complex is 1: 0.01-1, preferred 1: 0.04-0.4, more preferably 1: 0.08-0.2, the ratio of described magnesium compound and described solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml, in the described magnesium compound of magnesium compound solid and the mass ratio of described porous carrier is 1: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5, and 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.

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

10. alkene homopolymerization/copolymerization process, it is characterized in that, being major catalyst according to aforementioned aspect 9 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 complex is adjustable, can give full play to it obtains polyolefin product at catalysis in olefine polymerization performance.

Adopt method for preparing catalyst provided by the invention, owing to the complex solid product is fully obtaining after the post precipitation filtration washing drying under the precipitating reagent effect by mixed slurry, so the combination of key substance is comparatively tight in the catalyst.

Also find simultaneously, when employing load type non-metallocene catalyst that the present invention obtained and co-catalyst constitute catalyst system and catalyzing, narrow in the molecular weight distribution that catalysis in olefine polymerization obtains, and show significant comonomer effect during copolymerization, promptly under equal relatively condition, the copolymerization activity is higher than the homopolymerization activity.

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 complex are dissolved in the solvent, obtain the step of magnesium compound solution; Optional porous carrier through thermal activation treatment is mixed with described magnesium compound solution, obtain the step of mixed serum; With in described mixed serum, add precipitating reagent, 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 complex 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 complex 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,, make that the mol ratio in the described magnesium compound (solid) of Mg element and described Nonmetallocene complex reaches 1: 0.01-1, preferred 1: 0.04-0.4, more preferably 1: 0.08-0.2 as the consumption of described Nonmetallocene complex.

There is no particular limitation to the preparation time (being the dissolution time of described magnesium compound and described Nonmetallocene complex) 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 complex.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 complex is selected from the compound with following chemical structural formula:

According to this chemical structural formula, the part that forms coordinate bond with central metal atom M comprises n radicals X and m multidentate ligand (structural formula in the bracket).According to the chemical structural formula of described multidentate ligand, group A, D and E (coordination group) form coordinate bond with atom (such as hetero atoms such as N, O, S, Se and P) with described central metal atom M by the contained coordination of these groups.

According to the present invention, all parts (comprising described radicals X and described multidentate ligand) with the negative electrical charge sum absolute value and described central metal atom M positively charged absolute value identical.

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

At one more specifically in the embodiment, described Nonmetallocene complex be 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;

M is 1,2 or 3;

M is selected from periodic table of elements III-th family to XI family metallic atom, and preferred IV B family metallic atom is such as enumerating Ti (IV), Zr (IV), Hf (IV), Cr (III), Fe (III), Ni (II), Pd (II) or Co (II);

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

-NR ²³R ²⁴,-N (O) R ²⁵R ²⁶,

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;

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;

---represent coordinate bond, 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 IV B 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 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 radicals R that comprises with group ⁵) there is not substantial interference with the coordination process of described central metal atom M; In other words, limit by the chemical constitution of multidentate ligand 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.) complexation reaction takes place and form coordinate bond with described central metal atom M.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 or nitro (NO ₂) etc.

In the context of the present invention, limit by the chemical constitution of multidentate ligand 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 central metal atom M the coordination process and

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

In the context of the present invention, described boron-containing group is selected from BF ₄ ^-, (C ₆F ₅) ₄B ^-Or (R ⁴⁰BAr ₃) ^-Describedly contain aluminium base group and be selected from alkyl aluminum, AlPh ₄ ^-, AlF ₄ ^-, AlCl ₄ ^-, AlBr ₄ ^-, AlI ₄ ^-Or R ⁴¹AlAr ₃ ^-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 ⁵⁴, described Ar represents C ₆-C ₃₀Aryl, and R ⁴⁰To 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 complex, such as enumerating following compound:

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

Described Nonmetallocene complex further is preferably selected from following compound:

Described Nonmetallocene complex more preferably is selected from following compound:

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

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

Described Nonmetallocene complex or described multidentate ligand 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.

By described porous carrier is mixed with described magnesium compound solution, obtain mixed serum thus.

According to the present invention, the mixed process of described porous carrier and described magnesium compound solution can adopt usual way to carry out, and there is no particular limitation.Such as enumerating, at normal temperature to the preparation temperature of described magnesium compound solution, in described magnesium compound solution, be metered into described porous carrier, perhaps in described porous carrier, be metered into described magnesium compound solution, mix 0.1～8h, preferred 0.5～4h, optimum 1～2h (in case of necessity by stirring) gets final product.

According to the present invention,, make the mass ratio of described magnesium compound (in the magnesium compound solid that contains in the described magnesium compound solution) and described porous carrier reach 1: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5 as the consumption of described porous carrier.

According to the present invention, described mixed serum is a kind of half-dried system, does not have free liquid.Though unessential, in order to ensure the uniformity of system, this mixed serum preferably carries out certain hour (2～48h, preferred 4～24h, most preferably 6～18h) airtight leaving standstill after preparation.

Below described porous carrier is carried out specific description.

According to the present invention, as described porous carrier, such as can enumerate this area when making loaded catalyst as carrier and conventional those organic or inorganic porosu solids that use.

Particularly, as described organic porosu solid, such as enumerating olefin homo or copolymer, polyvinyl alcohol or its copolymer, cyclodextrin, (being total to) polyester, (being total to) polyamide, ryuron or copolymer, Voncoat R 3310 or copolymer, methacrylic acid ester homopolymer or copolymer, and styrene homopolymers or copolymer etc., and the partial cross-linked form of these homopolymers or copolymer, wherein preferably partial cross-linked (such as the degree of cross linking be at least 2% but less than 100%) styrene polymer.

Embodiment preferred according to the present invention, preferably on the surface of described organic porosu solid, have such as any one or the multiple active function groups that are selected from hydroxyl, primary amino radical, secondary amino group, sulfonic group, carboxyl, amide groups, the mono-substituted amide groups of N-, sulfoamido, the mono-substituted sulfoamido of N-, sulfydryl, acylimino and the hydrazide group wherein preferred carboxyl and hydroxyl.

Embodiment preferred according to the present invention is preferably carried out thermal activation treatment to described organic porosu solid before use.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under the inert atmosphere described organic porosu solid being carried out heat treated.Here said inert atmosphere be meant only contain extremely trace in the gas or do not contain can with the component of described organic porosu solid reaction.As described inert atmosphere, such as enumerating nitrogen or rare gas atmosphere, preferred nitrogen atmosphere.Because the poor heat resistance of organic porosu solid, thus this thermal activation process with the structure of not destroying described organic porosu solid itself with basic composition is prerequisite.Usually, the temperature of this thermal activation is 50～400 ℃, preferred 100～250 ℃, and the thermal activation time is 1～24h, preferred 2～12h.After the thermal activation treatment, described organic porosu solid need be preserved standby in malleation under the inert atmosphere

As described inorganic porous solid, such as the refractory oxides that can enumerate period of element Table II A, III A, IVA or IV B family metal (such as silica (being called silica or silica gel again), aluminium oxide, magnesia, titanium oxide, zirconia or thorium oxide etc.), perhaps any infusibility composite oxides of these metals (such as oxidation sial, oxidation magnalium, titanium oxide silicon, titanium oxide magnesium and titanium oxide aluminium etc.), and clay, molecular sieve (such as ZSM-5 and MCM-41), mica, imvite, bentonite and diatomite etc.As described inorganic porous solid, can also enumerate the oxide that generates by pyrohydrolysis by gaseous metal halide or gaseous silicon compound, such as the silica gel that obtains by the silicon tetrachloride pyrohydrolysis, perhaps aluminium oxide that obtains by the alchlor pyrohydrolysis etc.

As described inorganic porous solid, preferred silica, aluminium oxide, magnesia, oxidation sial, oxidation magnalium, titanium oxide silicon, titanium dioxide, molecular sieve and imvite etc., preferred especially silica.

According to the present invention, suitable silica can be by the conventional method manufacturing, it perhaps can be the commercial product that to buy arbitrarily, such as the Grace 955 that can enumerate Grace company, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, DavsionSyloid 245 and Aerosil812, the ES70 of Ineos company, ES70X, ES70Y, ES70W, ES757, EP10X and EP11, and CS-2133 of Pq Corp. and MS-3040.

Embodiment preferred according to the present invention preferably has hydroxyl isoreactivity functional group on the surface of described inorganic porous solid.

According to the present invention, in a preferred embodiment, preferably before use described inorganic porous solid is carried out thermal activation treatment.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under the inert atmosphere described inorganic porous solid being carried out heat treated.Here said inert atmosphere be meant only contain extremely trace in the gas or do not contain can with the component of described inorganic porous solid reaction.As described inert atmosphere, such as enumerating nitrogen or rare gas atmosphere, preferred nitrogen atmosphere.Usually, the temperature of this thermal activation is 200-800 ℃, and preferred 400～700 ℃, most preferably 400～650 ℃, heat time heating time is such as being 0.5～24h, preferred 2～12h, most preferably 4～8h.After the thermal activation treatment, described inorganic porous solid need be preserved standby in malleation under the inert atmosphere.

According to the present invention, there is no particular limitation to the surface area of described porous carrier, but be generally 10～1000m ²/ g (BET method mensuration), preferred 100～600m ²/ g; The pore volume of this porous carrier (determination of nitrogen adsorption) is generally 0.1～4cm ³/ g, preferred 0.2～2cm ³/ g, and preferred 1～500 μ m of its average grain diameter (laser particle analyzer mensuration), more preferably 1～100 μ m.

According to the present invention, described porous carrier can be a form arbitrarily, such as micropowder, granular, spherical, aggregation or other form.

According to the present invention, by in described mixed serum, being metered into precipitating reagent, solid matter is precipitated out from this mixed serum, promptly obtain load type non-metallocene catalyst of the present invention.

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 mixed serum, 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.

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 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,, make to reach 1: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5 in the described magnesium compound of magnesium compound solid and the mass ratio of described porous carrier as the consumption of described porous carrier.

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 IV B 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 IV B 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 complex adopts oxolane.Porous carrier adopts silica, i.e. silica gel, and model is the ES757 of Ineos company, the Nonmetallocene complex adopts structure to be

Compound.

At first silica gel is continued roasting 4h and thermal activation under 600 ℃, nitrogen atmosphere.

Take by weighing 5g anhydrous magnesium chloride and Nonmetallocene complex, dissolving fully under the normal temperature behind the adding tetrahydrofuran solvent, add silica gel then through thermal activation, stir after 2 hours, add the precipitating reagent hexane and make it precipitation, filter, wash 2 times, each precipitating reagent consumption evenly is heated under 90 ℃ and vacuumizes drying with addition is identical before, obtains load type non-metallocene catalyst.

Wherein proportioning is, magnesium chloride and oxolane proportioning are 1mol: 210ml; Magnesium chloride and Nonmetallocene complex mol ratio are 1: 0.08; The mass ratio of magnesium chloride and porous carrier is 1: 2, and precipitating reagent and oxolane volume proportion are 1: 1;

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

Embodiment 2

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

Porous carrier is changed into 955 of Grace company, continues roasting 8h and thermal activation under 400 ℃, nitrogen atmosphere.

The Nonmetallocene complex adopts

The solvent of dissolved magnesium compound and Nonmetallocene complex is changed into toluene, and precipitating reagent is changed into cyclohexane.

Wherein proportioning is, magnesium compound and toluene proportioning are 1mol: 150ml; Magnesium compound and Nonmetallocene complex mol ratio are 1: 0.15; The mass ratio of magnesium compound and porous carrier is 1: 4, and precipitating reagent is 1: 2 with the solvent volume ratio of dissolved magnesium compound and Nonmetallocene complex.

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

Embodiment 3

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

Porous carrier adopts alundum (Al.Alundum (Al is continued roasting 6h under 700 ℃, nitrogen atmosphere.

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

The solvent of dissolved magnesium compound and Nonmetallocene complex is changed into ethylbenzene, and precipitating reagent is changed into cycloheptane.

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 250ml; Magnesium compound and Nonmetallocene complex mol ratio are 1: 0.20; The mass ratio of magnesium compound and porous carrier is 1: 1, and precipitating reagent is 1: 0.80 with the solvent volume ratio of dissolved magnesium compound and Nonmetallocene complex.

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

Embodiment 4

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

Porous carrier adopts silica-magnesia mixed oxide (mass ratio 1: 1).The silica-magnesia mixed oxide is continued roasting 4h under 600 ℃, argon gas atmosphere.

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

The solvent of dissolved magnesium compound and Nonmetallocene complex is changed into dimethylbenzene, and precipitating reagent is changed into decane.

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 300ml; Magnesium compound and Nonmetallocene complex mol ratio are 1: 0.04; The mass ratio of magnesium compound and porous carrier is 1: 3, and precipitating reagent is 1: 2 with the solvent volume ratio of dissolved magnesium compound and Nonmetallocene complex.

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

Embodiment 5

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

The porous carrier adopting montmorillonite.Imvite is continued roasting 8h under 400 ℃, nitrogen atmosphere.

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

The solvent of dissolved magnesium compound and Nonmetallocene complex is changed into diethylbenzene.

Wherein proportioning is, the solvent burden ratio of magnesium compound and dissolved magnesium compound and Nonmetallocene complex is 1mol: 400ml; Magnesium compound and Nonmetallocene complex mol ratio are 1: 0.30; The mass ratio of magnesium compound and porous carrier is 1: 5.

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

Embodiment 6

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

Porous carrier adopts styrene.Styrene is continued oven dry 12h under 85 ℃, nitrogen atmosphere.

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

The solvent of dissolved magnesium compound and Nonmetallocene complex is changed into chlorotoluene.

Wherein proportioning is, magnesium compound and Nonmetallocene complex mol ratio are 1: 0.10; The mass ratio of magnesium compound and porous carrier is 1: 10.

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

Embodiment 7

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

Porous carrier adopts diatomite.Diatomite is continued roasting 8h under 500 ℃, nitrogen atmosphere.

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

Wherein proportioning is, the mass ratio of magnesium compound and porous carrier is 1: 0.5.

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

Embodiment 8

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 complex adopts

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

Embodiment 9

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)).

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

Embodiment 10

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)).

Load type non-metallocene catalyst is designated as CAT-10.

Comparative Examples 1-A

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

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

Catalyst is designated as CAT-1-A.

Comparative Examples 1-B

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

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

Catalyst is designated as CAT-1-B.

Application Example

With catalyst CAT-1～9 that make in the embodiment of the invention, CAT-1-A～B, carry out the homopolymerization and the copolymerization of ethene under the following conditions in accordance with the following methods respectively:

Homopolymerization is: 5 liters of polymerization autoclaves, and slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 1.5MPa, 85 ℃ of polymerization temperatures, the reactive metal mol ratio is 200 in co-catalyst and the catalyst, 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, continue to feed ethene and make the polymerization stagnation pressure constant at 1.5MPa.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 1.

Copolymerization is poly-to be: 5 liters of polymerization autoclaves, and slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 1.5MPa, 85 ℃ of polymerization temperatures, the reactive metal mol ratio is 200 in co-catalyst and the catalyst, 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 continues to feed ethene and makes the polymerization stagnation pressure constant in 1.5MPa.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 1.

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

By table 1 as seen, the molecular weight distribution that the load type non-metallocene catalyst polymerization for preparing with method provided by the invention obtains is very narrow, those skilled in the art know that the molecular weight of polyethylene that generally adopts the Ziegler-Natta catalyst polymerization to obtain is distributed in about 3～8.

Result of the test data by sequence number 1 in the contrast table 1 and sequence number 12,13 increase in the catalyst or reduce Nonmetallocene complex addition as can be known, and its activity increases thereupon or reduces, and the molecular weight distribution of polymer does not have variation substantially.Thereby illustrated that activity derives from the Nonmetallocene complex in load type non-metallocene catalyst provided by the present invention, the polymer performance that is obtained by polymerization is also determined by it.

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

2. according to the described preparation method of claim 1, it is characterized in that, described porous carrier is selected from olefin homo or copolymer, polyvinyl alcohol or its copolymer, cyclodextrin, polyester or copolyesters, polyamide or copolyamide, ryuron or copolymer, Voncoat R 3310 or copolymer, methacrylic acid ester homopolymer or copolymer, styrene homopolymers or copolymer, the partial cross-linked form of these homopolymers or copolymer, period of element Table II A, III A, the refractory oxides or the infusibility composite oxides of IV A or IV B family metal, clay, molecular sieve, mica, imvite, in bentonite and the diatomite one or more, be preferably selected from partial cross-linked styrene polymer, silica, aluminium oxide, magnesia, the oxidation sial, the oxidation magnalium, titanium dioxide, in molecular sieve and the imvite one or more more preferably are selected from silica.

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 complex is selected from one or more in the compound with following chemical structural formula:

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

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

-NR ²³R ²⁴,-N (O) R ²⁵R ²⁶,

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;

→ represent singly-bound or two key;

-represent covalent bond or ionic bond;

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

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 Ar represents C ₆-C ₃₀Aryl, and

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 complex is 1: 0.01-1, preferred 1: 0.04-0.4, more preferably 1: 0.08-0.2, the ratio of described magnesium compound and described solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml is 1 in the described magnesium compound of magnesium compound solid and the mass ratio of described porous carrier: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5, and 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.

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. load type non-metallocene catalyst, it is by making according to each described preparation method of claim 1-8.

10. alkene homopolymerization/copolymerization process, it is characterized in that, being major catalyst according to the described load type non-metallocene catalyst of claim 9, 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.