CN102964484A - Supported non-metallocene catalyst, preparation method and application - Google Patents

Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method. The supported non-metallocene catalyst is prepared by the steps of dissolving a non-metallocene ligand in a magnesium compound solution, performing an in-situ reaction with a chemical treatment agent, and dipping a solution of a non-metallocene complex. The preparation method is simple and feasible, the ingredients content of the non-metallocene is adjustable, and the copolymerization effect is substantial. The invention also relates to the application of the supported non-metallocene catalyst in olefin homopolymerisation/copolymerization. Compared with the prior art, the polymerization activity by catalysis of alkene is high, the bulk density of the polymer is high, and the molecular weight distribution is narrow and controllable.

Description

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

The application based on " national 11th Five-Year supporting plan problem " in the project of grinding.This project has obtained the great attention of the Ministry of Science and Technology and has supported energetically, its target is to form the polyolefin catalyst technology of new generation with independent intellectual property right, and improve domestic related products unification, improve China's polyolefine kind class, promote it to the future development of variation, seriation, customizations, high performance.

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 again luxuriant rear catalyst, the central atom of Primary Catalysts 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 excellent property of the polyolefin products of such catalyzer manufacturing, and low cost of manufacture.The non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, such as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and have cis alkyl or halogen metal division center, carry out easily alkene insertion and σ-key and shift, the easy alkylation of central metal is conducive to the generation at cation activity center; The title complex that forms has the geometric configuration of restriction, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key polarizes easily, more is conducive to polymerization and the copolymerization of alkene.

But homogeneous catalyst has been proved it in olefinic polyreaction has the active duration weak point, glue still easily, promotor methylaluminoxane consumption is high, and obtain the too low or too high weak point of polymericular 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 WO 03/010207 disclose a kind of alkene homopolymerization/catalyst for copolymerization or catalyst system, has widely alkene homopolymerization/copolymerization performance, but need higher promotor consumption during in olefinic polymerization at the disclosed catalyzer of this patent or catalyst system, could obtain suitable olefin polymerizating activity, and it is short to exist active duration in the polymerization process, the phenomenons such as the sticking still of polymkeric substance.

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

For patent ZL 01126323.7, ZL 02151294.9ZL 02110844.7 and the disclosed non-metallocene catalyst of WO03/010207, patent CN200310106156.x, CN200310106157.4, CN200410066070.3, CN200410066069.0,200510119401.x etc. provide various ways to carry out load to obtain load type non-metallocene catalyst.

Patent 200610026765.8 discloses a class single active center Z-N olefin polymerization catalysis.This catalyzer, obtains after processing through pretreated carrier (such as silica gel), metallic compound (such as titanium tetrachloride) and electron donor by adding in magnesium compound (such 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.

Patent 200610026766.2 is similar with it, discloses a class and has contained heteroatomic organic compound and the application in Ziegler-Natta catalyst thereof.

Patent 200910180601.4 discloses a kind of preparation method of load type non-metallocene catalyst, it is that magnesium compound and Nonmetallocene title complex are dissolved in the solvent, add through dry behind the porous support of thermal activation treatment, obtain load type non-metallocene catalyst.Patent 200910180602.9 discloses a kind of preparation method of load type non-metallocene catalyst, and it is that magnesium compound and Nonmetallocene title complex are dissolved in the solvent, and filtration washing is dry behind the adding precipitation agent, obtains load type non-metallocene catalyst.The supported catalyst that these two kinds of methods obtain all can obtain the narrower polymkeric substance of molecular weight distribution (the molecular weight distribution coefficient of polymkeric substance is about 2～3, and the molecular weight distribution coefficient that significantly is lower than the Ziegler-Natta catalyst preparation is 4～8 polymkeric substance) when carrying out olefinic polymerization catalysis.Obviously, the characteristic of polymkeric substance is that character by the Nonmetallocene title complex determines.

Chinese patent 200910180100.6,200910180607.1,200910180606.7,200910180605.2,200910180603.3,200910180604.8 disclosed load type non-metallocene catalyst preparation methods and above-mentioned patent are similar, what all use is that the carrier system that mixes fully mixes with the Nonmetallocene title complex, through super-dry or precipitation etc. non-chemically process process, obtain load type non-metallocene catalyst.Same character by Nonmetallocene title complex itself determines that the polymerization activity of such supported catalyst slightly is lower than Ziegler-Natta type catalyzer, and the particle form of polymkeric substance is difficult control also.

Chinese patent 200910210985.X discloses a kind of preparation method of load type non-metallocene catalyst, it is that magnesium compound and Nonmetallocene part are dissolved in the solvent, obtain the carrier modified after the drying, react with chemical processing agent and modification carrier, further process obtaining load type non-metallocene catalyst.Patent 200910210990.0 discloses a kind of preparation method of load type non-metallocene catalyst, it is that magnesium compound and Nonmetallocene part are dissolved in the solvent, add porous support, vacuumize the carrier that obtains modifying after the drying, react with chemical processing agent and modification carrier equally, further process obtaining load type non-metallocene catalyst.What these two kinds of methods adopted is that the Nonmetallocene part is pre-dispersed in carrier, the non-metallocene catalyst that obtains is better than the loading type single-site catalysts aspect polymerization activity, be better than the Zieger-Natta catalyzer aspect the polymer performance (such as molecular weight distribution).

Patent 200710162667.1,200710162676.0 disclosed load type non-metallocene catalyst preparation methods and above-mentioned patent are similar, what all use is that the Nonmetallocene part is pre-dispersed in carrier, then obtain load type non-metallocene catalyst with the chemical processing agent reaction, such catalyzer is better than the Zieger-Natta catalyzer aspect polymer performance.

Patent 200310106157.4 discloses a kind of preparation method of load type non-metallocene catalyst, it is the complex carrier of magnesium compound and porous support preparation to be contacted with chemical processing agent obtain a kind of Ziegler-Natta catalyst, and then with Nonmetallocene title complex contact preparation non-metallocene catalyst.Preparation method and the aforesaid method of patent 200710162677.5 disclosed load type non-metallocene catalysts are similar, also are to contact to prepare load type non-metallocene catalyst by Ziegler-Natta catalyst with the Nonmetallocene title complex.The catalyzer of these two kinds of method preparations increases significantly aspect the polymer performance with respect to Ziegler-Natta catalyst.

Although the polymer performance of load type non-metallocene catalyst preparation promotes to some extent with respect to Ziegler-Natta catalyst, but rangeability is less, fail to give full play to the Nonmetallocene ligands and complexes to the decisive role of polymer performance, thereby limited the industrial large-scale application of 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 finds through diligent research on the basis of existing technology, by making described load type non-metallocene catalyst with a kind of preparation method that original position load and dip loading are combined, can give full play to the Nonmetallocene title complex to the decisive role of polymer performance, can improve catalyst activity again, improve morphology, in order to solving foregoing problems, and finished thus the present invention.

In the preparation method of load type non-metallocene catalyst of the present invention, do not add proton donor (such as conventional those that use in this area).In addition, in the preparation method of load type non-metallocene catalyst of the present invention, do not add electron donor (such as in this area for this reason and the conventional compounds such as monoesters class, di-esters, two ethers, diones and diol-lipid that use).Moreover, in the preparation method of load type non-metallocene catalyst of the present invention, also need not harsh reaction requirement and reaction conditions.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 is dissolved in the presence of alcohol in the first solvent, obtains the step of magnesium compound solution;

Optional porous support, described magnesium compound solution through thermal activation treatment contacted with the Nonmetallocene part, obtain the step of the first mixed serum;

Described the first mixed serum of convection drying, the step of acquisition complex carrier;

Make the chemical processing agent and the reaction of described complex carrier that are selected from IVB family metallic compound, the step that obtains to modify complex carrier;

The Nonmetallocene title complex is contacted in the presence of the second solvent with described modification complex carrier, obtain the step of the second mixed serum; With

Described the second mixed serum of convection drying obtains the step of described load type non-metallocene catalyst.

2. according to the described preparation method of aforementioned either side, it is characterized in that, described porous support is selected from olefin homo or multipolymer, polyvinyl alcohol or its multipolymer, cyclodextrin, polyester or copolyesters, polymeric amide or copolyamide, ryuron or multipolymer, Voncoat R 3310 or multipolymer, methacrylic acid ester homopolymer or multipolymer, styrene homopolymers or multipolymer, the partial cross-linked form of these homopolymer or multipolymer, periodic table of elements IIA, IIIA, the refractory oxide of IVA or IVB family metal or infusibility composite oxides, clay, molecular sieve, mica, polynite, in wilkinite and the diatomite one or more, be preferably selected from partial cross-linked styrene polymer, silicon-dioxide, aluminum oxide, magnesium oxide, the oxidation sial, the oxidation magnalium, titanium dioxide, in molecular sieve and the polynite one or more more preferably are selected from silicon-dioxide.

3. according to the described preparation method of aforementioned either side, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide, alkoxyl group 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 the described preparation method of aforementioned either side, it is characterized in that described the first solvent is selected from C _5-12Alkane, C _5-12Naphthenic hydrocarbon, halo C _1-10Alkane, halo C _5-12Naphthenic hydrocarbon, C _6-12Aromatic hydrocarbon, halo C _6-12In aromatic hydrocarbon, ester and the ether one or more are preferably selected from C _5-12Alkane, C _5-12Naphthenic hydrocarbon, C _6-12In aromatic hydrocarbon and the tetrahydrofuran (THF) one or more most preferably are selected from tetrahydrofuran (THF) and the hexane one or more, and described alcohol is selected from C _1-30Fatty Alcohol(C12-C14 and C12-C18), C _6-30Aromatic alcohol and C _4-30In the alicyclic ring alcohol one or more, optional halogen atom or the C of being selected from of wherein said alcohol _1-6The substituting group of alkoxyl group replaces, and described alcohol is preferably selected from C _1-30In the aliphatic monobasic alcohol one or more more preferably are selected from ethanol, butanols and the 2-Ethylhexyl Alcohol one or more, and described the second solvent is selected from C _6-12Aromatic hydrocarbon, halo C _6-12Aromatic hydrocarbon, halo C _1-10In alkane, ester and the ether one or more, be preferably selected from toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and the tetrahydrofuran (THF) one or more, more preferably C _6-12In aromatic hydrocarbon, methylene dichloride and the tetrahydrofuran (THF) one or more.

5. according to the described preparation method of aforementioned either side, 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 Sauerstoffatom, 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, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, 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 linkage or ionic linkage;

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from independently of one another hydrogen, C 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 electron 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 atoms metal,

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

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 aforementioned either side, 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 described safing function group;

Described R ³⁷Be selected from hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or described 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 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;

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

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 R ⁴²To R ⁵⁴Be selected from independently of one another hydrogen, described C ₁-C ₃₀The C of alkyl, described replacement ₁-C ₃₀Alkyl or described 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 defines with aforementioned either side.

7. according to the described preparation method of aforementioned either side, it is characterized in that described Nonmetallocene title 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 atoms metal, preferred IVB family atoms metal, 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 Sauerstoffatom, 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, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, 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 Sauerstoffatom, 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 linkage or ionic linkage;

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

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from independently of one another hydrogen, C 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 electron 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 atoms metal,

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

Described Nonmetallocene title 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:

8. according to the described preparation method of aforementioned either side, 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 described safing function group;

Described R ³⁷Be selected from hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or described 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 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;

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

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 aluminum alkyls, 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 independently of one another hydrogen, described C ₁-C ₃₀The C of alkyl, described replacement ₁-C ₃₀Alkyl or described 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 defines with aforementioned either side.

9. according to the described preparation method of aforementioned either side, it is characterized in that, take the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene title complex as 1: 0.01-1, preferred 1: 0.04-0.4, more preferably 1: 0.08-0.2, take the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part as 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 the first solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml, take the mass ratio of the described magnesium compound of magnesium compound solid and described porous support as 1: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5, in the described magnesium compound of Mg element with take the mol ratio of the described chemical processing agent of IVB family metallic element as 1: 0.01-1, preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30, and take the mol ratio of the described magnesium compound of Mg element and described alcohol as 1: 0.02～4.00, preferred 1: 0.05～3.00, more preferably 1: 0.10～2.50.

10. according to the described preparation method of aforementioned either side, 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 halogenide, 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.

11. according to the described preparation method of aforementioned either side, also be included in make described Nonmetallocene title complex and described modification complex carrier contact before, with being selected from the step that helps the described modification complex carrier of chemical processing agent pre-treatment of aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

12. according to the described preparation method of aforementioned either side, it is characterized in that, described aikyiaiurnirsoxan beta is selected from methylaluminoxane, ethylaluminoxane, in isobutyl aluminium alkoxide and the normal-butyl alumina alkane one or more, more preferably be selected from methylaluminoxane and the isobutyl aluminium alkoxide one or more, and described aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminium, three n-pentyl aluminium, tri-n-hexyl aluminum, three isohexyl aluminium, in diethylmethyl aluminium and the dimethyl ethyl aluminium one or more, be preferably selected from trimethyl aluminium, triethyl aluminum, in tri-n-n-propyl aluminum and the triisobutyl aluminium one or more most preferably are selected from triethyl aluminum and the triisobutyl aluminium one or more.

13. according to the described preparation method of aforementioned either side, it is characterized in that, in the described magnesium compound of Mg element and the mol ratio that helps chemical processing agent take Al element described as 1: 0-1.0, preferred 1: 0-0.5, more preferably 1: 0.1-0.5.

14. a load type non-metallocene catalyst, it is to be made by the preparation method according to aforementioned either side.

15. alkene homopolymerization/copolymerization process, it is characterized in that, take according to aspect 14 described load type non-metallocene catalysts as Primary Catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more as promotor, make alkene homopolymerization or its poly-.

16. an alkene homopolymerization/copolymerization process is characterized in that, may further comprise the steps:

Described preparation method makes load type non-metallocene catalyst according to aforementioned either side, and

Take described load type non-metallocene catalyst as Primary Catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more as promotor, make alkene homopolymerization or copolymerization.

Technique effect

Preparation method's technique simple possible of load type non-metallocene catalyst of the present invention, and the charge capacity of Nonmetallocene part and title 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, because catalyzer prepares by Nonmetallocene part and IVB family chemical processing agent reaction in－situ and then two steps of load non-metallocene metal complexes, the controlled leeway of molar ratio of the constituent content of reactive metal and conventional reactive metal and Nonmetallocene title complex is large in the catalyzer, thereby effectively controls catalyst activity and polymer performance.

Method for preparing catalyst provided by the invention, the promotor consumption is few during catalysis in olefine polymerization, and can be by the change of polymerizing condition, the performance of Effective Raise Olefins Product Streams, the molecular weight distribution that obtains thus is narrow and bulk density high.

The present invention also finds, when the load type non-metallocene catalyst that employing the present invention obtains and promotor consist of catalyst system, narrow in the molecular weight distribution that catalysis in olefine polymerization obtains, and show significant comonomer effect during copolymerization, namely under relatively equal condition, Copolymerization activity is higher than the homopolymerization activity.

The present invention finds simultaneously, the preparation method of load type non-metallocene catalyst provided by the invention, the raising of magnesium compound content is conducive to improve catalyst activity, the increase of porous support content then helps to improve polymer stacks density, the molecular weight distribution that narrows improves the ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight.Therefore by regulating the two proportioning, just can regulate catalysis in olefine polymerization activity, polymer stacks density and molecular weight and distribution thereof.

Embodiment

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

In the context of the present invention, unless clearly definition is arranged in addition, perhaps this implication has exceeded those skilled in the art's understanding scope, and the hydrocarbon that 3 carbon atoms are above or hydrocarbon derivative group (such as propyl group, propoxy-, butyl, butane, butylene, butenyl, hexane etc.) all have implication identical with titled with prefix " just " time not titled with prefix " just " time.Such as, propyl group is generally understood as n-propyl, and butyl is generally understood as normal-butyl.

The present invention relates to a kind of preparation method of load type non-metallocene catalyst, may further comprise the steps: magnesium compound is dissolved in the presence of alcohol in the first solvent, obtains the step of magnesium compound solution; Optional porous support, described magnesium compound solution through thermal activation treatment contacted with the Nonmetallocene part, obtain the step of the first mixed serum; Described the first mixed serum of convection drying, the step of acquisition complex carrier; Make the chemical processing agent and the reaction of described complex carrier that are selected from IVB family metallic compound, the step that obtains to modify complex carrier; The Nonmetallocene title complex is contacted in the presence of the second solvent with described modification complex carrier, obtain the step of the second mixed serum; With described the second mixed serum of convection drying, obtain the step of described load type non-metallocene catalyst.

Below described magnesium compound is carried out specific description.

According to the present invention, term " magnesium compound " uses the common concept 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 group 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., preferred magnesium chloride wherein.

As described alkoxyl group magnesium halide, such as enumerating methoxyl group chlorination magnesium (Mg (OCH ₃) Cl), oxyethyl group magnesium chloride (Mg (OC ₂H ₅) Cl), propoxy-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), oxyethyl group magnesium bromide (Mg (OC ₂H ₅) Br), propoxy-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), oxyethyl group magnesium iodide (Mg (OC ₂H ₅) I), propoxy-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, oxyethyl group magnesium chloride and isobutoxy magnesium chloride.

As described alkoxyl magnesium, such as enumerating magnesium methylate (Mg (OCH ₃) ₂), magnesium ethylate (Mg (OC ₂H ₅) ₂), propoxy-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-magnesium (Mg (i-C ₄H ₉) ₂) etc., wherein preferred magnesium ethide and normal-butyl magnesium.

As described alkyl halide magnesium, such as enumerating methylmagnesium-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-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), selenium alkynide (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-iodate magnesium (Mg (i-C ₄H ₉) I) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl-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 propoxy-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 methylate (Mg (OCH ₃) (C ₂H ₅)), ethyl magnesium ethylate (Mg (OC ₂H ₅) (C ₂H ₅)), ethyl propoxy-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 methylate (Mg (OCH ₃) (C ₃H ₇)), propyl group magnesium ethylate (Mg (OC ₂H ₅) (C ₃H ₇)), propyl group propoxy-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 methylate (Mg (OCH ₃) (C ₄H ₉)), normal-butyl magnesium ethylate (Mg (OC ₂H ₅) (C ₄H ₉)), normal-butyl propoxy-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-magnesium methylate (Mg (OCH ₃) (i-C ₄H ₉)), isobutyl-magnesium ethylate (Mg (OC ₂H ₅) (i-C ₄H ₉)), isobutyl-propoxy-magnesium (Mg (OC ₃H ₇) (i-C ₄H ₉)), isobutyl-n-butoxy magnesium (Mg (OC ₄H ₉) (i-C ₄H ₉)) and isobutyl-isobutoxy magnesium (Mg (i-OC ₄H ₉) (i-C ₄H ₉)) etc., preferred butyl magnesium ethylate wherein.

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 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.

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

According to this step, make magnesium compound in the presence of alcohol, be dissolved in suitable solvent (hereinafter referred to as the solvent or the first solvent that are used for dissolving described magnesium compound), thereby obtain described magnesium compound solution.

As described the first solvent, such as enumerating C _5-12Alkane, C _5-12Naphthenic hydrocarbon, halo C _1-10Alkane, halo C _5-12Naphthenic hydrocarbon, C _6-12Aromatic hydrocarbon, halo C _6-12Aromatic hydrocarbon, ester and ether equal solvent.

As described C _5-12Alkane, such as enumerating pentane, hexane, heptane, octane, nonane and decane etc., wherein preferred hexane, heptane and decane, most preferably hexane.

As described C _5-12Naphthenic hydrocarbon is such as enumerating hexanaphthene, pentamethylene, suberane, cyclodecane and cyclononane etc., most preferably hexanaphthene.

As described halo C _1-10Alkane is such as enumerating methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane and three n-butyl bromide etc.

As described halo C _5-12Naphthenic hydrocarbon is such as enumerating chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, bromo cyclononane and bromo cyclodecane etc.

As described C _6-12Aromatic hydrocarbon is such as enumerating toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene.

As described halo C _6-12Aromatic hydrocarbon is such as enumerating chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene etc.

As described ester, such as enumerating methyl-formiate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butylacetate, methyl propionate, ethyl propionate, butyl propionate, butyl butyrate etc.

As described ether, such as enumerating ether, methyl ethyl ether, tetrahydrofuran (THF) etc.

Wherein, preferred C _5-12Alkane, C _5-12Naphthenic hydrocarbon, C _6-12Aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF) and hexane.

Preferably, described the first solvent also demonstrates dissolving power to hereinafter described Nonmetallocene part.

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

According to the present invention, term " alcohol " refers to hydrocarbon chain (such as C _1-30Hydrocarbon) at least one hydrogen atom on is replaced by hydroxyl and the compound that obtains.

As described alcohol, such as enumerating C _1-30Fatty Alcohol(C12-C14 and C12-C18) (preferred C _1-30Aliphatic monobasic alcohol), C _6-30Aromatic alcohol (preferred C _6-30The aromatic series monohydroxy-alcohol) and C _4-30Alicyclic ring alcohol (preferred C _4-30Alicyclic monohydroxy-alcohol), preferred C wherein _1-30Aliphatic monobasic alcohol or C _2-8Aliphatic monobasic alcohol, more preferably ethanol and butanols.In addition, described alcohol can be chosen wantonly and is selected from halogen atom or C _1-6The substituting group of alkoxyl group replaces.

As described C _1-30Fatty Alcohol(C12-C14 and C12-C18) is such as enumerating methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, amylalcohol, 2-methyl amyl alcohol, 2-ethylpentanol, 2-hexyl butanols, hexanol and 2-Ethylhexyl Alcohol etc., wherein preferred alcohol, butanols and 2-Ethylhexyl Alcohol.

As described C _6-30Aromatic alcohol, such as enumerating phenylcarbinol, phenylethyl alcohol and methylbenzyl alcohol etc., preferred phenylethyl alcohol wherein.

As described C _4-30Alicyclic ring alcohol, such as enumerating hexalin, cyclopentanol, ring octanol, methylcyclopentanol, ethyl cyclopentanol, propyl group cyclopentanol, methyl-cyclohexanol, ethyl cyclohexanol, propyl group hexalin, methyl ring octanol, ethyl ring octanol and propyl group ring octanol etc., wherein preferred hexalin and methyl-cyclohexanol.

As the described alcohol that is replaced by halogen atom, such as enumerating trichlorine methyl alcohol, ethapon and three Mecorals etc., preferred trichlorine methyl alcohol wherein.

The described alcohol that replaces as alkoxy, such as enumerating glycol-ether, ethylene glycol-n-butyl ether and 1-butoxy-2-propyl alcohol etc., preferred glycol-ether wherein.

These alcohol can be used alone, and also can multiple mixing use.When using with the form of multiple mixing, the ratio between any two kinds of alcohol in the described alcohol mixture can be to determine arbitrarily, not special the restriction.

In order to prepare described magnesium compound solution, described magnesium compound can be added in the mixed solvent that is formed by described the first solvent and described alcohol and dissolve, perhaps described magnesium compound is added in described the first solvent, and simultaneously or add subsequently alcohol and dissolve, but be not limited to this.

There is no particular limitation to the preparation time (being the dissolution time of described magnesium compound) 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.This stirring can be adopted any form, such as stirring rake (rotating speed is generally 10～1000 rev/mins) etc.As required, sometimes can promote dissolving by suitable heating (but top temperature must be lower than the boiling point of described solvent and described alcohol).

According to the present invention, term " Nonmetallocene title complex " is a kind of single site olefin polymerization catalysts for metallocene catalyst, do not contain the cyclopentadienyl or derivatives thereofs such as luxuriant ring, fluorenes ring or indenes ring in the structure, and with promotor (such as hereinafter described those) combination the time, can demonstrate the organometallics (therefore described Nonmetallocene title complex is also sometimes referred to as the non-metallocene olefin polymerization title complex) of olefinic polymerization catalysis activity.This compound comprises the polydentate ligand (preferably tridentate ligand or more polydentate ligand) that central metal atom and at least one and described central metal atom are combined with coordinate bond, and term " Nonmetallocene part " is aforesaid polydentate 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 atoms metal generation coordination reaction of the IVB family metallic compound that uses as chemical processing agent among atom (such as heteroatomss such as N, O, S, Se and P) and the present invention, form thus the title complex (being Nonmetallocene title complex of the present invention) of atoms metal centered by this IVB family atoms metal.

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 Sauerstoffatom, 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, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, 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 linkage or ionic linkage.

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from independently of one another hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl (preferred halo alkyl wherein, 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 (preferred halo alkyl wherein, such as-CH ₂Cl and-CH ₂CH ₂Cl) or the phenyl ring that replaces of safing function group.

R ⁵Be selected from lone-pair electron 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 atoms metal.

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 ²⁶Described 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 ³⁴Described sulfur-containing group is selected from-SR ³⁵,-T-SR ³⁵,-S (O) R ³⁶Or-T-SO ₂R ³⁷The described seleno group that contains is selected from-SeR ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹Or-T-Se (O) R ³⁹Described 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.

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-), 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 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom, such as pyridyl, pyrryl, furyl or thienyl etc.

According to the present invention, in the context of the present invention, according to the particular case 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 with 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, perhaps also chooses wantonly and comprise R with group ⁵) there is not substantial interference with the coordination process of central metal atom (aforementioned IVB family atoms metal); In other words, limit by the chemical structure of part of the present invention, these substituting groups do not have ability or have no chance (such as the impact that is subject to steric hindrance etc.) forms coordinate bond with described IVB family's atoms metal generation coordination reaction.Generally speaking, described inert substituent is selected from aforesaid halogen or C ₁-C ₃₀Alkyl (preferred C ₁-C ₆Alkyl is such as isobutyl-).

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, be selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group such as enumerating, contain tin group, C ₁-C ₁₀Ester group and nitro (NO ₂) at least a etc.

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

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

(2) coordination ability with described IVB family atoms metal 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 atoms metal.

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 independently of one another hydrogen, aforesaid C 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.Wherein the definition of group T is the same.

As described Nonmetallocene part, such as enumerating following compound:

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 sheets is introduced these documents at this point as a reference.

Below described porous support is carried out specific description.

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

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

Preferred embodiment according to the present invention, preferably on the surface of described Porous-Organic solid with such as any one or the multiple active function groups that are selected from hydroxyl, primary amino, secondary amino group, sulfonic group, carboxyl, amide group, the mono-substituted amide group of N-, sulfoamido, the mono-substituted sulfoamido of N-, sulfydryl, acylimino and the hydrazide group, at least a in preferred carboxyl and the hydroxyl wherein.

According to an embodiment of the invention, before use described Porous-Organic 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 Porous-Organic solid being carried out heat treated.Here said inert atmosphere refer to only contain in the gas extremely trace or do not contain can with the component of described Porous-Organic solid reaction.As described inert atmosphere, such as enumerating nitrogen or rare gas atmosphere, preferred nitrogen atmosphere.Because the poor heat resistance of Porous-Organic solid, thus this thermal activation process with the structure of not destroying described Porous-Organic 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 Porous-Organic solid need to save backup in malleation under the inert atmosphere.

As described inorganic porous solid, such as the refractory oxide that can enumerate periodic table of elements IIA, IIIA, IVA or IVB family metal (such as silicon-dioxide (being called again silicon oxide or silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium white or Thorotrast 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, polynite, wilkinite and diatomite etc.As described inorganic porous solid, can also enumerate the oxide compound that is generated by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound, such as the silica gel that is obtained by the silicon tetrachloride pyrohydrolysis, the aluminum oxide that is perhaps obtained by the aluminum chloride pyrohydrolysis etc.

As described inorganic porous solid, preferred silicon-dioxide, aluminum oxide, magnesium oxide, oxidation sial, oxidation magnalium, titanium oxide silicon, titanium dioxide, molecular sieve and polynite etc., particularly preferably silicon-dioxide.

According to the present invention, suitable silicon-dioxide can be by the ordinary method manufacturing, it perhaps can be the commerical prod 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, Davsion Syloid 245 and Aerosil812, the ES70 of Ineos company, ES70X, ES70Y, ES70W, ES757, EP10X and EP11, and the CS-2133 of Pq Corp. and MS-3040.

Preferred embodiment according to the present invention, preferably on the surface of described inorganic porous solid with hydroxyl isoreactivity functional group.

According to the present invention, in one embodiment, 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 refer to only contain in the gas extremely trace 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-up 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 to save backup in malleation under the inert atmosphere.

According to the present invention, there is no particular limitation to the surface-area of described porous support, but be generally 10～1000m ²/ g (BET method mensuration), preferred 100～600m ²/ g; The pore volume of this porous support (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 median size (laser particle analyzer mensuration), more preferably 1～100 μ m.

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

According to the present invention, described optional porous support, described magnesium compound solution through thermal activation treatment contacted with described Nonmetallocene part, obtain the first mixed serum.

When making described the first mixed serum, there is no particular limitation to the way of contact of described optional porous support, described magnesium compound solution and described Nonmetallocene part through thermal activation treatment and engagement sequence etc., such as enumerating described optional porous support through thermal activation treatment is mixed first with described magnesium compound solution, and then to the scheme that wherein adds described Nonmetallocene part; Make described optional scheme of mixing simultaneously through porous support, described magnesium compound solution and the described Nonmetallocene part of thermal activation treatment; Described Nonmetallocene part and described magnesium compound are dissolved in foregoing the first solvent, make thus the mixing solutions (sometimes being also referred to as hereinafter magnesium compound solution) of magnesium compound and Nonmetallocene part, and then make scheme that described optional porous support through thermal activation treatment mixes with described mixing solutions etc.

In addition, in order to make described the first mixed serum, such as can be at normal temperature to the temperature of the boiling point that is lower than employed any solvent, make the contact reacts of porous support, described magnesium compound solution and the described Nonmetallocene part of described optional process thermal activation treatment carry out 0.1～8h, preferred 0.5～4h, optimum 1～2h (in case of necessity by stirring) gets final product.

At this moment, the first mixed serum that obtains is a kind of system of pulpous state.Although unessential, in order to ensure the homogeneity of system, this first mixed serum preferably carries out certain hour (2～48h, preferred 4～24h, most preferably 6～18h) airtight leaving standstill afterwards in preparation.

By to described mixed serum convection drying, can obtain a kind of solid product of good fluidity, i.e. described complex carrier.

At this moment, described convection drying can adopt ordinary method to carry out, such as heat drying under drying under dry under the inert gas atmosphere, the vacuum atmosphere or the vacuum atmosphere etc., and heat drying under the preferred vacuum atmosphere wherein.Drying temperature is generally 30～160 ℃, preferred 60～130 ℃, is generally 2～24h time of drying, but sometimes is not limited to this.

Below described chemical processing agent is carried out specific description.

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

As described IVB family metallic compound, to be selected from IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, IVB family metal alkyl halides and IVB family metal alkoxide halid at least a such as enumerating.

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 halogenide, such as the compound that can enumerate following formula:

M(OR ¹) _mX _nR ² _4-m-n

Wherein:

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

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

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

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

R ¹And R ²Be selected from independently of one another C _1-10Alkyl is such as methyl, ethyl, propyl group, normal-butyl, isobutyl-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 tetrachloride (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-titanium (Ti (i-C ₄H ₉) ₄), tetra-n-butyl titanium (Ti (C ₄H ₉) ₄), triethyl methyltitanium (Ti (CH ₃) (CH ₃CH ₂) ₃), diethyl-dimethyl titanium (Ti (CH ₃) ₂(CH ₃CH ₂) ₂), trimethylammonium 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), trimethylammonium isobutyl-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 isobutyl-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), trimethylammonium 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 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-zirconium (Zr (i-C ₄H ₉) ₄), tetra-n-butyl zirconium (Zr (C ₄H ₉) ₄), triethyl methylcyclopentadienyl zirconium (Zr (CH ₃) (CH ₃CH ₂) ₃), diethyl-dimethyl zirconium (Zr (CH ₃) ₂(CH ₃CH ₂) ₂), trimethylammonium 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), trimethylammonium isobutyl-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 isobutyl-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), trimethylammonium 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 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-hafnium (Hf (i-C ₄H ₉) ₄), tetra-n-butyl hafnium (Hf (C ₄H ₉) ₄), triethyl methylcyclopentadienyl hafnium (Hf (CH ₃) (CH ₃CH ₂) ₃), diethyl-dimethyl hafnium (Hf (CH ₃) ₂(CH ₃CH ₂) ₂), trimethylammonium 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), trimethylammonium isobutyl-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 isobutyl-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), trimethylammonium 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 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 oxyethyl group 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 oxyethyl group 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 oxyethyl group 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 oxyethyl group 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 trimethylammonium titanium chloride (TiCl (CH ₃) ₃), triethyl 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 dichloride (TiCl ₂(CH ₃) ₂), diethyl titanium dichloride (TiCl ₂(CH ₃CH ₂) ₂), diisobutyl titanium dichloride (TiCl ₂(i-C ₄H ₉) ₂), three normal-butyl chlorination titanium (TiCl (C ₄H ₉) ₃), methyl titanous chloride (Ti (CH ₃) Cl ₃), ethyl titanous chloride (Ti (CH ₃CH ₂) Cl ₃), isobutyl-titanous chloride (Ti (i-C ₄H ₉) Cl ₃), normal-butyl titanous chloride (Ti (C ₄H ₉) Cl ₃);

Trimethylammonium titanium bromide (TiBr (CH ₃) ₃), triethyl 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-titanium tribromide (Ti (i-C ₄H ₉) Br ₃), normal-butyl titanium tribromide (Ti (C ₄H ₉) Br ₃);

Trimethylammonium zirconium chloride (ZrCl (CH ₃) ₃), triethyl 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-tri-chlorination zirconium (Zr (i-C ₄H ₉) Cl ₃), normal-butyl tri-chlorination zirconium (Zr (C ₄H ₉) Cl ₃);

Trimethylammonium zirconium bromide (ZrBr (CH ₃) ₃), triethyl 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-tribromide zirconium (Zr (i-C ₄H ₉) Br ₃), normal-butyl tribromide zirconium (Zr (C ₄H ₉) Br ₃);

Trimethylammonium hafnium chloride (HfCl (CH ₃) ₃), triethyl 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-tri-chlorination hafnium (Hf (C ₄H ₉) Cl ₃), normal-butyl tri-chlorination hafnium (Hf (C ₄H ₉) Cl ₃);

Trimethylammonium bromination hafnium (HfBr (CH ₃) ₃), triethyl 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-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 halogenide, 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-Butoxyl titanium-chlorides (TiCl (OC ₄H ₉) ₃), dimethoxy titanium dichloride (TiCl ₂(OCH ₃) ₂), diethoxy titanium dichloride (TiCl ₂(OCH ₃CH ₂) ₂), two isobutoxy titanium dichloride (TiCl ₂(i-OC ₄H ₉) ₂), three n-Butoxyl titanium-chlorides (TiCl (OC ₄H ₉) ₃), methoxyl group titanous chloride (Ti (OCH ₃) Cl ₃), oxyethyl group titanous chloride (Ti (OCH ₃CH ₂) Cl ₃), isobutoxy titanous chloride (Ti (i-C ₄H ₉) Cl ₃), n-butoxy titanous chloride (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), oxyethyl group 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), oxyethyl group 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), oxyethyl group 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), oxyethyl group 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), oxyethyl group 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.

According to the present invention, make the chemical processing agent and the described complex carrier reaction (chemical treatment reaction) that are selected from described IVB family metallic compound, obtain the modification complex carrier.

When described chemical processing agent is liquid state at normal temperatures, can use described chemical processing agent by the mode that in the reaction object (such as aforesaid complex carrier) that remains to utilize this chemical processing agent to process, directly drips the described chemical processing agent of predetermined amount.When described chemical processing agent when being solid-state at normal temperatures, for measure with easy to operate for the purpose of, preferably use described chemical processing agent with the form of solution.Certainly, when described chemical processing agent is liquid state at normal temperatures, sometimes also can use described chemical processing agent with the form of solution as required, not special the restriction.

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

Particularly, can enumerate C _5-12Alkane, C _5-12Naphthenic hydrocarbon, halo C _5-12Alkane, halo C _5-12Naphthenic hydrocarbon, C _6-12Aromatic hydrocarbons or halo C _6-12Aromatic hydrocarbons etc., such as enumerating pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, toluene, ethylbenzene, dimethylbenzene, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro undecane, chlorinated dodecane, chlorocyclohexane, chlorotoluene, chloro ethylbenzene and xylene monochloride etc., wherein preferred pentane, hexane, decane, hexanaphthene and toluene, most preferably hexane and toluene.

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

In addition, there is no particular limitation to the concentration of described chemical processing agent in its solution, can suitably select as required, as long as it can realize implementing described chemical treatment with the described chemical processing agent of predetermined amount.As previously mentioned, if chemical processing agent is liquid, can directly carry out described processing with chemical processing agent, but use after also it can being modulated into the chemical treatment agent solution.

That the volumetric molar concentration of described chemical processing agent in its solution generally is set as 0.01～1.0mol/L, but is not limited to this easily.

As carrying out described chemically treated method, such as enumerating, be in the situation of solid-state (such as zirconium tetrachloride) at chemical processing agent, the solution that at first prepares described chemical processing agent, then in pending reaction object (such as aforesaid complex carrier), add the described solution that (the preferred dropping) contains the described chemical processing agent of predetermined amount, to carry out the chemical treatment reaction.Be in the situation of liquid (such as titanium tetrachloride) at chemical processing agent, can be directly the described chemical processing agent of predetermined amount be added in (the preferred dropping) pending reaction object (such as aforesaid complex carrier), to carry out the chemical treatment reaction, perhaps after this chemical processing agent is prepared into solution, in pending reaction object (such as aforesaid complex carrier), add the described solution that (the preferred dropping) contains the described chemical processing agent of predetermined amount, to carry out the chemical treatment reaction.

Generally speaking, described chemical treatment reaction (in case of necessity by stirring) was carried out 0.5～24 hour, preferred 1～8 hour, more preferably got final product in 2～6 hours.

After the chemical treatment reaction finishes, by filtering, wash and drying, can obtain through chemically treated product, i.e. described modification complex carrier.

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

Described drying can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or the vacuum, and heat drying method, most preferably heat drying method under the vacuum under preferred rare gas element desiccating method or the vacuum.The temperature range of described drying is generally normal temperature to 140 ℃, is generally 2-20 hour time of drying, but is not limited to this.

That is, according to the present invention, after the reaction of using described chemical processing agent finishes, by aforesaid filtration, washing and drying, the processing product that obtains is separated fully, and then used this processing product to carry out next step reaction or processing.

So far, according to the present invention, make the reaction of described chemical processing agent and described complex carrier, cause aforementioned Nonmetallocene part generation coordination reaction contained on described chemical processing agent and this complex carrier, thereby at the Nonmetallocene title complex (original position load reaction) of original position generation atoms metal centered by this IVB family atoms metal on this complex carrier, this is of the present invention one large feature.

According to the present invention, employed Nonmetallocene title complex is selected from the compound with following chemical structural formula among the preparation method:

According to this chemical structural formula, the part that forms coordinate bond with central metal atom M comprises n radicals X and m polydentate ligand (structural formula in the bracket).According to the chemical structural formula of described polydentate ligand, group A, D and E (coordination group) form coordinate bond with atom (such as heteroatomss 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 polydentate ligand) with the positively charged absolute value of absolute value and the described central metal atom M of negative charge sum identical.

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

At one more specifically in the embodiment, described Nonmetallocene title 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 atoms metal, preferred IVB family atoms metal is such as enumerating Ti (IV), Zr (IV), Hf (IV), Cr (III), Fe (III), Ni (II), Pd (II) or Co (II);

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 Sauerstoffatom, 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, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, 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 Sauerstoffatom, 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 linkage or ionic linkage;

---represent coordinate bond, covalent linkage or ionic linkage.

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from independently of one another hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl (preferred halo alkyl wherein, 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 (preferred halo alkyl wherein, 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 electron 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 atoms metal.

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 ²⁶Described 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 ³⁴Described sulfur-containing group is selected from-SR ³⁵,-T-SR ³⁵,-S (O) R ³⁶Or-T-SO ₂R ³⁷The described seleno group that contains is selected from-SeR ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹Or-T-Se (O) R ³⁹Described 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.

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-), 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 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom, such as pyridyl, pyrryl, furyl or thienyl etc.

According to the present invention, in the context of the present invention, according to the particular case 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 with 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, perhaps also chooses wantonly and comprise radicals R 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 structure of polydentate ligand of the present invention, these substituting groups do not have ability or have no chance (such as the impact that is subject to steric hindrance etc.) coordination reaction occurs and form coordinate bond with described central metal atom M.Generally speaking, described inert substituent is such as being selected from aforesaid halogen or C ₁-C ₃₀Alkyl (preferred C ₁-C ₆Alkyl is such as isobutyl-).

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, be selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group such as enumerating, contain tin group, C ₁-C ₁₀Ester group or nitro (NO ₂) at least a etc.

In the context of the present invention, limit by the chemical structure of polydentate ligand of the present invention, described safing function group has following characteristics:

(1) do not disturb the coordination process of described group A, D, E, F, Y or Z and described central metal atom M, 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 aluminum alkyls, 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, wherein Ar represents C ₆-C ₃₀Aryl.R ⁴⁰To R ⁵⁴Be selected from independently of one another hydrogen, aforesaid C 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.Wherein, the definition of group T is the same.

As described Nonmetallocene title complex, such as enumerating following compound:

Described Nonmetallocene title complex is preferably selected from following compound:

Described Nonmetallocene title complex further is preferably selected from following compound:

Described Nonmetallocene title complex more preferably is selected from following compound:

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

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

Described Nonmetallocene title complex or described polydentate 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 sheets is introduced these documents at this point as a reference.

Then, make described modification complex carrier in the presence of the second solvent, contact (contact reacts) with described Nonmetallocene title complex, can obtain described the second mixed serum.

When making described the second mixed serum, there is no particular limitation to the way of contact of described modification complex carrier and described Nonmetallocene title complex (and described second solvent) and engagement sequence etc., such as enumerating described modification complex carrier is mixed first with described Nonmetallocene title complex, and then to the scheme that wherein adds described the second solvent; Described Nonmetallocene title complex is dissolved in described the second solvent, makes thus the Nonmetallocene complex solution, and then make scheme that described modification complex carrier mixes with described Nonmetallocene complex solution etc., wherein the preferred latter.

In addition, in order to make described the second mixed serum, such as can be at normal temperature to the temperature of the boiling point that is lower than employed any solvent, described modification complex carrier and the described Nonmetallocene title complex contact reacts (in case of necessity by stirring) in the presence of described the second solvent was carried out 0.5～24 hour, preferred 1～8 hour, more preferably got final product in 2～6 hours.

At this moment, the second mixed serum that obtains is a kind of system of pulpous state.Although unessential, in order to ensure the homogeneity of system, this second mixed serum preferably carries out certain hour (2～48h, preferred 4～24h, most preferably 6～18h) airtight leaving standstill afterwards in preparation.

According to the present invention, when making described the second mixed serum, there is no particular limitation to described the second solvent (below be sometimes referred to as dissolving Nonmetallocene title complex solvent), needs only it and can dissolve described Nonmetallocene title complex.As described the second solvent, such as enumerating C _6-12Aromatic hydrocarbon, halo C _6-12Aromatic hydrocarbon, halo C _1-10In alkane, ester and the ether one or more.Specifically such as enumerating toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and tetrahydrofuran (THF) etc.Wherein, preferred C _6-12Aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).

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

When making described the second mixed serum or described Nonmetallocene complex solution, can use as required stirring (rotating speed of this stirring is generally 10～500 rev/mins).

According to the present invention, to the consumption of described the second solvent without any restriction, get final product with the amount that described Nonmetallocene title complex fully contacts so long as be enough to realize described modification complex carrier.Such as, being easily, described Nonmetallocene title complex is generally 0.01～0.25 grams per milliliter with respect to the ratio of described the second solvent, preferred 0.05～0.16 grams per milliliter, but sometimes be not limited to this.

Then, by to described the second mixed serum convection drying, can obtain a kind of solid product of good fluidity, i.e. load type non-metallocene catalyst of the present invention.

At this moment, described convection drying can adopt ordinary method to carry out, such as heat drying under drying under dry under the inert gas atmosphere, the vacuum atmosphere or the vacuum atmosphere etc., and heat drying under the preferred vacuum atmosphere wherein.Carry out under the temperature (being generally 30～160 ℃, preferred 60～130 ℃) that the boiling point of any solvent that described drying generally contains in than described mixed serum is low 5～15 ℃, and be generally 2～24h time of drying, but sometimes be not limited to this.

Special embodiment according to the present invention, before the preparation method of load type non-metallocene catalyst of the present invention also is included in and makes described Nonmetallocene title complex and described modification complex carrier contacts, with the step that helps the described modification complex carrier of chemical processing agent pre-treatment (pre-treatment step) that is selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

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

According to the present invention, as the described chemical processing agent that helps, such as enumerating aikyiaiurnirsoxan beta and aluminum alkyls.

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 independently of one another C ₁-C ₈Alkyl, preferable methyl, ethyl and isobutyl-, 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, ethylaluminoxane, 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 aluminum alkyls, such as enumerating the compound shown in the following general formula:

Al(R) ₃

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

Particularly, as described aluminum alkyls, such as enumerating trimethyl aluminium (Al (CH ₃) ₃), triethyl aluminum (Al (CH ₃CH ₂) ₃), tri-n-n-propyl aluminum (Al (C ₃H ₇) ₃), triisopropylaluminiuand (Al (i-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), tri-n-hexyl aluminum (Al (C ₆H ₁₃) ₃), three isohexyl 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 aluminum alkylss can be used alone, and perhaps are used in combination multiple with ratio arbitrarily.

According to the present invention, as the described chemical processing agent that helps, can only adopt described aikyiaiurnirsoxan beta, also can only adopt described aluminum alkyls, but also can adopt any mixture of described aikyiaiurnirsoxan beta and described aluminum alkyls.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 processing agent that helps generally is to use with the form of solution.When the described solution that helps chemical processing agent of preparation, to this moment employed solvent there is no particular limitation, as long as it can dissolve this and help chemical processing agent.

Particularly, can enumerate C _5-12Alkane, C _5-12Naphthenic hydrocarbon, halo C _5-12Alkane, halo C _5-12Naphthenic hydrocarbon, C _6-12Aromatic hydrocarbons or halo C _6-12Aromatic hydrocarbons etc., such as enumerating pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, toluene, ethylbenzene, dimethylbenzene, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro undecane, chlorinated dodecane, chlorocyclohexane, chlorotoluene, chloro ethylbenzene and xylene monochloride etc., wherein preferred pentane, hexane, decane, hexanaphthene and toluene, most preferably hexane and toluene.

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

It in addition, helps the concentration of chemical processing agent in its solution there is no particular limitation described, can suitably select as required, as long as can realize carrying out described pre-treatment with the described chemical processing agent that helps of predetermined amount.

Through described pre-treatment step, obtain through pretreated modification complex carrier thus.Then, according to aforementioned identical mode the pretreated modification complex carrier of described process is contacted in the presence of the second solvent with described Nonmetallocene title complex, just described modification complex carrier is replaced with the pretreated modification complex carrier of described process and get final product again.

That is, according to describe before complete identical mode and carry out described contact reacts, just described modification complex carrier is replaced with the pretreated modification complex carrier of described process and gets final product, and similarly obtain described the second mixed serum.

As the method for carrying out described pre-treatment step, such as enumerating, at first prepare the described solution that helps chemical processing agent, then to intending being metered into (the preferred dropping) described chemical treatment agent solution (the described chemical processing agent that helps that wherein contains predetermined amount) that helps with described helping in the pretreated described modification complex carrier of chemical processing agent, perhaps add described modification complex carrier to the described chemical treatment agent solution amount of falling into a trap that helps, form thus reaction mixture.At this moment, temperature of reaction is generally-40～60 ℃, and preferred-30～30 ℃, the reaction times is generally 1～8h, preferred 2～6h, most preferably 3～4h (in case of necessity by stirring).Then, by filtration, washing and optionally drying, from this reaction mixture, isolate the pre-treatment product.

Perhaps, according to circumstances, also can be without this separation and be directly used in follow-up reactions steps with the form of mixed solution.At this moment, owing to contained a certain amount of solvent in the described mixed solution, so the solvent load that relates in can the described subsequent reactions step of corresponding minimizing.

According to the present invention, described filtration, washing and drying can adopt ordinary method to carry out, and wherein washer solvent can adopt and dissolve described used identical solvent when helping chemical processing agent.As required, this washing is generally carried out 1～8 time, and preferred 2～6 times, most preferably 2～4 times.Described drying can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or the vacuum, and heat drying method, most preferably heat drying method under the vacuum under preferred rare gas element desiccating method or the vacuum.The temperature range of described drying is generally normal temperature to 140 ℃, is generally 2-20 hour time of drying, but is not limited to this.

According to the present invention, as the consumption of described Nonmetallocene title complex, so that reach 1 in the mol ratio of the described magnesium compound (solid) of Mg element and described Nonmetallocene title complex: 0.01-1, preferred 1: 0.04-0.4, more preferably 1: 0.08-0.2.

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

According to the present invention, as described be used to dissolving described magnesium compound solvent or the consumption of the first solvent, so that the ratio of described magnesium compound (solid) and described solvent reaches 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml.

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

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

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

According to the present invention, consumption as the described alcohol that is used with described solvent be used to dissolving described magnesium compound, so that in the mol ratio of the described magnesium compound (solid) of Mg element and described alcohol reach 1: 0.02～4.00, preferred 1: 0.05～3.00, more preferably 1: 0.10～2.50.

Known to those skilled in the artly be that aforementioned all method steps all preferably carries out under the condition of anhydrous anaerobic basically.Here the said basically anhydrous anaerobic content that refers to water and oxygen in the system continues less than 100ppm.And load type non-metallocene catalyst of the present invention needs to save backup in the presence of the pressure-fired rare gas element (such as nitrogen, argon gas, helium etc.) in confined conditions in preparation afterwards usually.

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

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, catalyzer and alkene etc.), can directly be suitable for conventional known those in this area, not special restriction, the description thereof will be omitted at this.

According to homopolymerization/copolymerization process of the present invention, take load type non-metallocene catalyst of the present invention as Primary Catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more as promotor, make alkene homopolymerization or copolymerization.

Primary Catalysts and promotor can be to add first Primary Catalysts to the adding mode in the polymerization reaction system, and then the adding promotor, perhaps add first promotor, and then add Primary Catalysts, or both contact first after the mixing and add together, perhaps add simultaneously respectively.Primary Catalysts and promotor 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 polyreaction, the reinforced pipeline of preferred multichannel adds simultaneously continuously, and for the intermittence type polymerization reaction, adds together in same reinforced pipeline after preferably both mix first, perhaps in same reinforced pipeline, add first promotor, and then add Primary Catalysts.

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, substance law and vapor phase process etc., wherein preferred slurries method and vapor phase process.

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 ₁₂Monoolefine 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 vinylbenzene etc.; As described cyclic olefin, such as enumerating 1-cyclopentenes and norbornylene etc.; As described diolefin, such as enumerating Isosorbide-5-Nitrae-divinyl, 2,5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc.; And as described other ethylenically unsaturated compounds, such as enumerating vinyl acetate 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 promotor is selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, wherein preferred aikyiaiurnirsoxan beta and aluminum alkyls.

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 independently of one another C ₁-C ₈Alkyl, preferable methyl, ethyl and isobutyl-, 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, ethylaluminoxane, 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 aluminum alkyls, such as enumerating the compound shown in the following general formula:

Al(R) ₃

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

Particularly, as described aluminum alkyls, such as enumerating trimethyl aluminium (Al (CH ₃) ₃), triethyl aluminum (Al (CH ₃CH ₂) ₃), tri-n-n-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), tri-n-hexyl aluminum (Al (C ₆H ₁₃) ₃), three isohexyl 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-n-n-propyl aluminum and triisobutyl aluminium, further preferred triethyl aluminum and triisobutyl aluminium, and triethyl aluminum most preferably.

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

As described haloalkyl aluminium, such as enumerating the compound shown in the following general formula:

Al(R) _nX _3-n

Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from independently of one another C ₁-C ₈Alkyl, preferable methyl, ethyl and isobutyl-, most preferable.Radicals X is halogen, preferred chlorine.N is 1 or 2.

Particularly, as described haloalkyl aluminium, such as enumerating a Chlorodimethyl aluminium (Al (CH ₃) ₂Cl), dichloromethyl aluminium (Al (CH ₃) Cl ₂)), aluminium diethyl monochloride (Al (CH ₃CH ₂) ₂Cl), ethyl aluminum dichloride (Al (CH ₃CH ₂) Cl ₂), a chlorine dipropyl aluminium (Al (C ₃H ₇) ₂Cl), two chloropropyl aluminium (Al (C ₃H ₇) Cl ₂)), a chlorine di-n-butyl aluminium (Al (C ₄H ₉) ₂Cl), dichloro n-butylaluminum (Al (C ₄H ₉) Cl ₂), a chloro-di-isobutyl aluminum (Al (i-C ₄H ₉) ₂Cl), dichloro aluminium isobutyl (Al (i-C ₄H ₉) Cl ₂), a chlorine two n-pentyl aluminium (Al (C ₅H ₁₁) ₂Cl), dichloro n-pentyl aluminium (Al (C ₅H ₁₁) Cl ₂), a chlorine diisoamyl aluminium (Al (i-C ₅H ₁₁) ₂Cl), dichloro isopentyl aluminium (Al (i-C ₅H ₁₁) Cl ₂), a chlorine di-n-hexyl aluminium (Al (C ₆H ₁₃) ₂Cl), dichloro n-hexyl aluminium (Al (C ₆H ₁₃) Cl ₂), a chlorine two isohexyl aluminium (Al (i-C ₆H ₁₃) ₂Cl), dichloro isohexyl aluminium (Al (i-C ₆H ₁₃) Cl ₂),

Chloromethyl aluminium triethyl (Al (CH ₃) (CH ₃CH ₂) Cl), chloromethyl propyl group aluminium (Al (CH ₃) (C ₃H ₇) Cl), chloromethyl n-butylaluminum (Al (CH ₃) (C ₄H ₉) Cl), chloromethyl aluminium isobutyl (Al (CH ₃) (i-C ₄H ₉) Cl), a chloroethyl propyl group aluminium (Al (CH ₂CH ₃) (C ₃H ₇) Cl), a chloroethyl n-butylaluminum (AlCH ₂CH ₃) (C ₄H ₉) Cl), chloromethyl aluminium isobutyl (AlCH ₂CH ₃) (i-C ₄H ₉) Cl) etc., wherein preferred aluminium diethyl monochloride, ethyl aluminum dichloride, a chlorine di-n-butyl aluminium, dichloro n-butylaluminum, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl, a chlorine di-n-hexyl aluminium, dichloro n-hexyl aluminium, further preferred chlorodiethyl aluminium, ethyl aluminum dichloride and a chlorine di-n-hexyl aluminium, and aluminium diethyl monochloride most preferably.

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

As 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 promotor can be used alone, and also can be as required be used in combination multiple aforesaid promotor, not special restriction with ratio arbitrarily.

According to the present invention, the difference (such as slurry polymerization) 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 methylene dichloride), C _6-12Naphthenic hydrocarbon (hexanaphthene, suberane, cyclooctane, cyclononane or cyclodecane), C _6-20Aromatic hydrocarbon (such as toluene and dimethylbenzene) etc.Wherein, preferably using pentane, hexane, heptane and cyclohexane give is described polymerization solvent, most preferably hexane.

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 0.4～3MPa, but sometimes be not limited to this.According to the present invention, polymeric reaction temperature is generally-40 ℃～200 ℃, and preferred 10 ℃～100 ℃, more preferably 40 ℃～95 ℃, but sometimes be not limited to this.

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.In situation about existing, the dividing potential drop of hydrogen can be 0.01%～99% of described polymerization pressure, and is preferred 0.01%～50%, but sometimes is not limited to this.

According to the present invention, when carrying out described alkene homopolymerization/copolymerization process, be generally 1～1000 in the described promotor of aluminium or boron and mol ratio in the described load type non-metallocene catalyst of described central metal atom: 1, preferred 10～500: 1, more preferably 15～300: 1, but sometimes be not limited to this.

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 GB 1636-79.

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 or title complex adopts analyses.

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

Molecular weight Mw, the Mn of polymkeric substance and molecular weight distribution (Mw/Mn) adopt the GPC V2000 type gel chromatography analyser of U.S. WATERS company to measure, and are solvent with 1,2,4-trichlorobenzene, and the temperature during mensuration is 150 ℃.

The viscosity-average molecular weight of polymkeric substance 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 thermostatic bath medium is No. 300 silicone oil, dilution is perhydronaphthalene with solvent, measuring temperature is 135 ℃) measure the limiting viscosity of described polymkeric substance, then calculate the viscosity-average molecular weight Mv of described polymkeric substance according to following formula.

Mv＝5.37×10 ⁴×[η] ^1.37

Wherein, η is limiting viscosity.

Embodiment 1

Magnesium compound adopts Magnesium Chloride Anhydrous, and the Nonmetallocene part adopts structure to be

Compound, the first solvent adopts hexane, alcohol adopts ethanol, porous support adopts silicon-dioxide, i.e. silica gel, model is the ES757 of Ineos company, at first silica gel is continued roasting 4h and thermal activation under 600 ℃, nitrogen atmosphere.IVB family chemical processing agent adopts titanium tetrachloride (TiCl ₄), the second solvent adopts methylene dichloride, and the Nonmetallocene title complex adopts structure to be

Compound.

Take by weighing 5 gram magnesium compounds, after joining the first solvent, add again pure and mild Nonmetallocene part, dissolving obtains magnesium compound solution fully at normal temperatures, then adds porous support, stirs after 2 hours, obtain the first mixed serum, then homogeneous heating to 90 ℃ directly vacuumizes drying, obtains complex carrier.

The complex carrier that makes is joined in the hexane solvent, and normal temperature is added dropwise to IVB family chemical processing agent in lower 30 minutes, and then homogeneous heating to 60 ℃ isothermal reaction is after 2 hours, filter hexane solvent washing 3 times, each 60ml, under 60 ℃, vacuumize drying at last, obtain modifying complex carrier.

At room temperature, the Nonmetallocene title complex is joined in the second solvent, then add and modify complex carrier, stirred 4 hours, airtight leaving standstill after 12 hours directly vacuumizes drying again, obtains load type non-metallocene catalyst.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 2; In the Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.08; With an alcohol mole proportioning be 1: 2; With the proportioning of the first solvent hexane be 1mol: 210ml; With the chemical processing agent mol ratio be 1: 0.20; The mol ratio of magnesium compound and Nonmetallocene title complex is 1: 0.08.

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

Embodiment 2

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

Modify complex carrier with before the Nonmetallocene title complex contact, first through helping the processing of chemical processing agent triethyl aluminum to obtain pretreated modification complex carrier.

Namely, to modify complex carrier joins in the hexane solvent, slowly drip again and help the chemical processing agent triethyl aluminum (concentration is 0.88mol/L, hexane solution), 60 ℃ of lower stirrings after 2 hours are filtered, hexane washing 3 times, each 60ml, under 60 ℃, vacuumize drying at last, obtain pretreated modification complex carrier.Wherein magnesium compound is 1: 0.2 with helping the mole proportioning of chemical processing agent.

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

Embodiment 3

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

Modify complex carrier with before the Nonmetallocene title complex contact, first through helping the processing of chemical processing agent methylaluminoxane to obtain pretreated modification complex carrier.

Namely, to modify complex carrier joins in the toluene solvant, slowly drip again and help the chemical processing agent methylaluminoxane (concentration is 10wt%, toluene solution), 60 ℃ of lower stirrings after 2 hours are filtered, toluene wash 3 times, each 60ml, under 100 ℃, vacuumize drying at last, obtain pretreated modification complex carrier.Wherein magnesium compound is 1: 0.4 with helping the mole proportioning of chemical processing agent.

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

Embodiment 4

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

Magnesium compound changes isobutoxy magnesium chloride (Mg (i-OC into ₄H ₉) Cl), alcohol changes propyl carbinol into, and the first solvent is changed into toluene, and the Nonmetallocene part adopts Porous support is changed into 955 of Grace company, continues roasting 8h and thermal activation under 400 ℃, nitrogen atmosphere.Chemical processing agent changes zirconium tetrachloride (ZrCl into ₄).

The Nonmetallocene title complex adopts The second solvent changes toluene into, and the first mixed serum is changed into and directly vacuumize drying under 100 ℃.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 1; In the Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.04; With an alcohol mole proportioning be 1: 1; With the proportioning of the first solvent be 1mol: 150ml; With the chemical processing agent mol ratio be 1: 0.30; The mol ratio of magnesium compound and Nonmetallocene title complex is 1: 0.10.

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

Embodiment 5

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

Magnesium compound is changed into anhydrous magnesium bromide (MgBr ₂), alcohol is changed into 2-Ethylhexyl Alcohol, and the first solvent and the second solvent are changed into tetrahydrofuran (THF), and the Nonmetallocene part adopts Porous support adopts aluminium sesquioxide.Aluminium sesquioxide is continued roasting 6h under 700 ℃, nitrogen atmosphere.Chemical processing agent changes titanium tetrabromide (TiBr into ₄),

The Nonmetallocene title complex adopts

The first mixed serum is changed into and directly vacuumize drying under 110 ℃.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 5; In the Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.2; With an alcohol mole proportioning be 1: 0.7; With the proportioning of the first solvent be 1mol: 280ml; With the chemical processing agent mol ratio be 1: 0.10; The mol ratio of magnesium compound and Nonmetallocene title complex is 1: 0.05.

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

Embodiment 6

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

Magnesium compound is changed into magnesium ethylate (Mg (OC ₂H ₅) ₂), the first solvent is changed into dimethylbenzene, and the Nonmetallocene part adopts Porous support adopts silica-magnesia mixed oxide (mass ratio 1: 1).The silica-magnesia mixed oxide is continued roasting 4h under 600 ℃, argon gas atmosphere.

The Nonmetallocene title complex adopts

Alcohol changes trichlorine methyl alcohol into.The chemical processing agent of IVB family metallic compound is changed into tetraethyl-titanium (Ti (CH ₃CH ₂) ₄), the first mixed serum is changed into and directly vacuumize drying under 120 ℃.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 10; In the Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.05; With an alcohol mole proportioning be 1: 0.7; With the proportioning of the first solvent be 1mol: 200ml; With the chemical processing agent mol ratio be 1: 0.15; The mol ratio of magnesium compound and Nonmetallocene title complex is 1: 0.04.

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

Embodiment 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 first solvent is changed into diethylbenzene, and alcohol is changed into phenylethyl alcohol, and the Nonmetallocene part adopts

The porous support adopting montmorillonite.Polynite is continued roasting 8h under 400 ℃, nitrogen atmosphere.The chemical processing agent of IVB family metallic compound is changed into tetra-n-butyl titanium (Ti (C ₄H ₉) ₄), the Nonmetallocene title complex adopts

The first mixed serum is changed into and directly vacuumize drying under 130 ℃.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 3; In the Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.4; With an alcohol mole proportioning be 1: 1.5; With the chemical processing agent mol ratio be 1: 0.50; Magnesium compound and the first solvent burden ratio are 1mol: 400ml; The mol ratio of magnesium compound and Nonmetallocene title complex is 1: 0.01.

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 ethylmagnesium chloride (Mg (C ₂H ₅) Cl), alcohol changes hexalin into, and the first solvent is changed into hexanaphthene, and porous support adopts the polystyrene of partial cross-linked (degree of crosslinking is 30%).This polystyrene is continued oven dry 12h under 85 ℃, nitrogen atmosphere.The Nonmetallocene part adopts

The Nonmetallocene title complex adopts

The chemical processing agent of IVB family metallic compound is changed into three isobutoxy titanium chloride (TiCl (i-OC ₄H ₉) ₃).

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 0.5; In the Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.01; With an alcohol mole proportioning be 1: 2.5; With the proportioning of the first solvent hexane be 1mol: 210ml; With the chemical processing agent mol ratio be 1: 0.20; The mol ratio of magnesium compound and Nonmetallocene title complex is 1: 0.20.

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 normal-butyl magnesium ethylate (Mg (OC ₂H ₅) (C ₄H ₉)), the first solvent is changed into chlorotoluene, and alcohol changes methyl-cyclohexanol into, and the Nonmetallocene part adopts

Porous support adopts diatomite.Diatomite is continued roasting 8h under 500 ℃, nitrogen atmosphere.The chemical processing agent of IVB family metallic compound is changed into purity titanium tetraethoxide (Ti (OCH ₃CH ₂) ₄), the Nonmetallocene title complex adopts

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 oxyethyl group magnesium chloride (Mg (OC ₂H ₅) Cl), the first solvent is changed into ethylbenzene, and alcohol changes glycol-ether into, and the Nonmetallocene part adopts

Porous support adopts titanium dioxide.Titanium dioxide is continued roasting 6h under 300 ℃, nitrogen atmosphere.

The Nonmetallocene title complex adopts

The chemical processing agent of IVB family metallic compound is changed into diethyl-dimethyl titanium (Ti (CH ₃) ₂(CH ₃CH ₂) ₂), the second solvent is changed into tetrahydrofuran (THF).

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

Reference example A

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

Do not add the Nonmetallocene part in the load type non-metallocene catalyst preparation process;

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

Reference example B

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

Omit in the load type non-metallocene catalyst preparation process and modify the step that complex carrier contacts with the Nonmetallocene title complex;

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

Reference example C

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

Magnesium compound and Nonmetallocene title complex proportioning are changed into 1: 0.16;

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

Reference example D

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

Magnesium compound and porous support mass ratio are changed into 1: 5;

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

Reference example E

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

Magnesium compound and porous support mass ratio are changed into 1: 0.2;

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

Application Example

The load type non-metallocene catalyst CAT-1 that makes in the embodiment of the invention～10, CAT-A～E are carried out respectively homopolymerization and the copolymerization of ethene under the following conditions in accordance with the following methods:

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 times.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, then add 20mg load type non-metallocene catalyst and catalyst mixture, add again hydrogen to 0.2MPa, continue at last to pass into ethene and make the polymerization stagnation pressure constant in 0.8MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry rear weighing quality.The particular case of this polyreaction 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 times.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, then add 20mg load type non-metallocene catalyst and catalyst mixture, disposable adding hexene-1 comonomer 50g, add again hydrogen to 0.2MPa, continue at last to pass into ethene and make the polymerization stagnation pressure constant in 0.8MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry rear weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.

The preparation ultrahigh molecular weight polyethylene(UHMWPE) 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, 2 hours reaction times.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, promotor is 100 with catalyst activity metal molar ratio, continues at last to pass into ethene and makes the polymerization stagnation pressure constant in 0.5MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry rear weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 2.

By as seen from Table 1, the molecular weight distribution that the load type non-metallocene catalyst polymerization for preparing with method provided by the invention obtains is narrower, those skilled in the art know that the molecular weight of polyethylene that generally adopts the Ziegler-Natta catalyst polymerization to obtain distributes greater than 5.

By sequence number in the table 11 and 3,5 and 7,8 and 10 test-results data as can be known, increase the consumption of promotor, namely improve promotor and catalyst activity metal molar than the time, impact active on 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 promotor consumption just can obtain high olefin polymerizating activity; And the polymkeric substance such as resulting polyethylene has good polymer morphology and high polymer bulk density thus.

Sequence number 1 and 2 in the contrast table 1,5 and 6,8 and 9 test-results data are as can be known, after the copolymerization, catalyst activity has increase by a relatively large margin, thereby explanation adopts the load type non-metallocene catalyst of method preparation provided by the invention to have comparatively significant comonomer effect.

By sequence number 1 in the contrast table 1 and Comparative Examples sequence number 20, and sequence number 1 and 9 test-results data are as can be known in the table 2, increase the add-on of Nonmetallocene title complex in the catalyzer, although polymer stacks density decreases, but its activity increases thereupon, molecular weight distribution narrows down, sequence number 1 and Comparative Examples sequence number 18 and 19 in the associative list 1, do not add the Nonmetallocene part or do not add the Nonmetallocene title complex in sequence number 1 and contrast sequence number 7 and 8 catalyst preparation process in the table 2, catalyst activity, polymer stacks density, and polymericular weight will broaden, and the ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight all decreases.Therefore can illustrate, can obtain the catalyzer of different activities and polymer performance by the add-on that changes the Nonmetallocene ligands and complexes.

By sequence number 1 in the contrast table 1 and Comparative Examples sequence number 21 and 22, and in the table 2 sequence number 1 and Comparative Examples 10 and 11 the test-results data as can be known, the proportioning of magnesium compound and porous support in reduction and the increase catalyzer, catalyst activity reduces or increases, polymer stacks density increases or reduces, polymericular weight narrows down or broadens, thereby the raising that magnesium compound content is described is conducive to improve catalyst activity, the increase of porous support content then helps to improve polymer stacks density, the molecular weight distribution that narrows improves the ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight.Therefore one skilled in the art will appreciate that by regulating the two proportioning, just can regulate catalysis in olefine polymerization activity, polymer stacks density and molecular weight and distribution thereof.

Although 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 embodiments, but determined 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 (12)

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

Magnesium compound is dissolved in the presence of alcohol in the first solvent, obtains the step of magnesium compound solution;

Optional porous support, described magnesium compound solution through thermal activation treatment contacted with the Nonmetallocene part, obtain the step of the first mixed serum;

Described the first mixed serum of convection drying, the step of acquisition complex carrier;

Make the chemical processing agent and the reaction of described complex carrier that are selected from IVB family metallic compound, the step that obtains to modify complex carrier;

The Nonmetallocene title complex is contacted in the presence of the second solvent with described modification complex carrier, obtain the step of the second mixed serum; With

Described the second mixed serum of convection drying obtains the step of described load type non-metallocene catalyst,

Wherein said preparation method is optional also be included in make described Nonmetallocene title complex and described modification complex carrier contact before, usefulness is selected from the step that helps the described modification complex carrier of chemical processing agent pre-treatment of aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

2. according to preparation method claimed in claim 1, it is characterized in that, described porous support is selected from olefin homo or multipolymer, polyvinyl alcohol or its multipolymer, cyclodextrin, polyester or copolyesters, polymeric amide or copolyamide, ryuron or multipolymer, Voncoat R 3310 or multipolymer, methacrylic acid ester homopolymer or multipolymer, styrene homopolymers or multipolymer, the partial cross-linked form of these homopolymer or multipolymer, periodic table of elements IIA, IIIA, the refractory oxide of IVA or IVB family metal or infusibility composite oxides, clay, molecular sieve, mica, polynite, in wilkinite and the diatomite one or more, be preferably selected from partial cross-linked styrene polymer, silicon-dioxide, aluminum oxide, magnesium oxide, the oxidation sial, the oxidation magnalium, titanium dioxide, in molecular sieve and the polynite one or more more preferably are selected from silicon-dioxide.

3. according to preparation method claimed in claim 1, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide, alkoxyl group 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 preparation method claimed in claim 1, it is characterized in that described the first solvent is selected from C _5-12Alkane, C _5-12Naphthenic hydrocarbon, halo C _1-10Alkane, halo C _5-12Naphthenic hydrocarbon, C _6-12Aromatic hydrocarbon, halo C _6-12In aromatic hydrocarbon, ester and the ether one or more are preferably selected from C _5-12Alkane, C _5-12Naphthenic hydrocarbon, C _6-12In aromatic hydrocarbon and the tetrahydrofuran (THF) one or more most preferably are selected from tetrahydrofuran (THF) and the hexane one or more, and described alcohol is selected from C _1-30Fatty Alcohol(C12-C14 and C12-C18), C _6-30Aromatic alcohol and C _4-30In the alicyclic ring alcohol one or more, optional halogen atom or the C of being selected from of wherein said alcohol _1-6The substituting group of alkoxyl group replaces, and described alcohol is preferably selected from C _1-30In the aliphatic monobasic alcohol one or more more preferably are selected from ethanol, butanols and the 2-Ethylhexyl Alcohol one or more, and described the second solvent is selected from C _6-12Aromatic hydrocarbon, halo C _6-12Aromatic hydrocarbon, halo C _1-10In alkane, ester and the ether one or more, be preferably selected from toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and the tetrahydrofuran (THF) one or more, more preferably C _6-12In aromatic hydrocarbon, methylene dichloride and the tetrahydrofuran (THF) one or more.

5. according to preparation method claimed in 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 Sauerstoffatom, 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, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, 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 linkage or ionic linkage;

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from independently of one another hydrogen, C 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 electron 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 atoms metal,

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

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 preparation method claimed in 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 described safing function group;

Described R ³⁷Be selected from hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or described 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 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;

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

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 R ⁴²To R ⁵⁴Be selected from independently of one another hydrogen, described C ₁-C ₃₀The C of alkyl, described replacement ₁-C ₃₀Alkyl or described 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 defines with claim 5.

7. according to preparation method claimed in claim 1, it is characterized in that described Nonmetallocene title 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 atoms metal, preferred IVB family atoms metal, 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 Sauerstoffatom, 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, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, 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 Sauerstoffatom, 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 linkage or ionic linkage;

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

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from independently of one another hydrogen, C 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 electron 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 atoms metal,

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

Described Nonmetallocene title 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:

8. according to preparation method claimed in claim 7, 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 described safing function group;

Described R ³⁷Be selected from hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or described 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 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;

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

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 aluminum alkyls, 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 independently of one another hydrogen, described C ₁-C ₃₀The C of alkyl, described replacement ₁-C ₃₀Alkyl or described 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 defines with claim 7.

9. according to preparation method claimed in claim 1, it is characterized in that, take the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene title complex as 1: 0.01-1, preferred 1: 0.04-0.4, more preferably 1: 0.08-0.2, take the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part as 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 the first solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml, take the mass ratio of the described magnesium compound of magnesium compound solid and described porous support as 1: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5, in the described magnesium compound of Mg element with take the mol ratio of the described chemical processing agent of IVB family metallic element as 1: 0.01-1, preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30, take the mol ratio of the described magnesium compound of Mg element and described alcohol as 1: 0.02～4.00, preferred 1: 0.05～3.00, more preferably 1: 0.10～2.50, and in the described magnesium compound of Mg element and the mol ratio that helps chemical processing agent take Al element described as 1: 0-1.0, preferred 1: 0-0.5, more preferably 1: 0.1-0.5.

10. according to preparation method claimed in 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 halogenide, 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.

11. a load type non-metallocene catalyst, it is by making according to each described preparation method of claim 1-10.

12. alkene homopolymerization/copolymerization process, it is characterized in that, take according to the described load type non-metallocene catalyst of claim 11 as Primary Catalysts, to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more as promotor, make alkene homopolymerization or copolymerization.