CN102964484B

CN102964484B - Supported non-metallocene catalyst, preparation method and application

Info

Publication number: CN102964484B
Application number: CN201110259336.6A
Authority: CN
Inventors: 任鸿平; 李传峰; 郭峰; 阚林; 柏基业; 马忠林; 陈韶辉; 汪开秀; 王亚明; 杨爱武
Original assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Priority date: 2011-08-31
Filing date: 2011-08-31
Publication date: 2014-12-10
Anticipated expiration: 2031-08-31
Also published as: CN102964484A

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 the 11th Five-Year supporting plan problem > > of < < country 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, at some aspect of performance, reach, 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.Non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and there is cis alkyl or halogen metal division center, easily carry out 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 forming has the geometric configuration of restriction, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key easily polarizes, and is more conducive to polymerization and the copolymerization of alkene.

But homogeneous catalyst has been proved it in olefinic polyreaction has that active duration is short, easily sticky still, promotor methylaluminoxane consumption are high, and obtain the too low or too high weak point of polymericular weight, only can, 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, there is alkene homopolymerization/copolymerization performance widely, but at the disclosed catalyzer of this patent or catalyst system, need higher promotor consumption during in olefinic polymerization, could obtain suitable olefin polymerizating activity, and it is short to exist active duration in polymerization process, the phenomenons such as the sticky still of polymkeric substance.

Common way be by 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 and even avoided caking or the cruelly poly-phenomenon in polymerization process, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, can make it meet more polymerization technique process, 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.

The open Liao Yi class of patent 200610026765.8 single active center Z-N olefin polymerization catalysis.This catalyzer is usingd the salicylic alidehyde imine derivative of the salicylic alidehyde imine that contains coordinating group or replacement as electron donor, by adding after pretreated carrier (as silica gel), metallic compound (as titanium tetrachloride) and electron donor are processed and obtain in magnesium compound (as magnesium chloride)/tetrahydrofuran solution.

Patent 200610026766.2 is similar with it, discloses a class containing 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 solvent, add after the porous support of thermal activation treatment and be dried, 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 solvent, adds after precipitation agent filtration washing dry, 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, the polymkeric substance that the molecular weight distribution coefficient of significantly preparing lower than Ziegler-Natta catalyst is 4～8) when carrying out olefinic polymerization catalysis.Obviously, the characteristic of polymkeric substance is that character by Nonmetallocene title complex determines.

The disclosed load type non-metallocene catalyst preparation method of Chinese patent 200910180100.6,200910180607.1,200910180606.7,200910180605.2,200910180603.3,200910180604.8 and above-mentioned patent are similar, what all use is that the carrier system mixing fully mixes with Nonmetallocene title complex, through super-dry or precipitation etc. non-chemically process process, obtain load type non-metallocene catalyst.By the character of Nonmetallocene title complex itself, determined equally, the polymerization activity of such supported catalyst is slightly lower than Ziegler-Natta type catalyzer, and the particle form of polymkeric substance is more 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 solvent, after dry, obtain the carrier of modifying, with chemical processing agent, react with modification carrier, further process and obtain 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 solvent, add porous support, vacuumize the carrier that obtains modification after being dried, with chemical processing agent, react with modification carrier equally, further process and obtain load type non-metallocene catalyst.What these two kinds of methods adopted is that Nonmetallocene part is pre-dispersed in carrier, the non-metallocene catalyst obtaining is better than loading type single-site catalysts aspect polymerization activity, aspect polymer performance (as molecular weight distribution), is being better than Zieger-Natta catalyzer.

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

Patent 200310106157.4 discloses a kind of preparation method of load type non-metallocene catalyst, it is complex carrier that magnesium compound is prepared with porous support 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, are also to contact to prepare load type non-metallocene catalyst by Ziegler-Natta catalyst with Nonmetallocene title complex.Catalyzer prepared by these two kinds of methods increases significantly aspect polymer performance with respect to Ziegler-Natta catalyst.

Although polymer performance prepared by load type non-metallocene catalyst promotes to some extent with respect to Ziegler-Natta catalyst, but rangeability is less, fail to give full play to the decisive role of Nonmetallocene ligands and complexes to polymer performance, thereby limited the industrial large-scale application of load type non-metallocene catalyst.

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

Summary of the invention

The inventor finds through diligent research on the basis of existing technology, by manufacturing described load type non-metallocene catalyst by a kind of preparation method that original position load and dip loading are combined, can give full play to the decisive role of Nonmetallocene title complex to polymer performance, can improve catalyst activity again, improve morphology, in order to solve foregoing problems, and completed 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, reaction requirement and reaction conditions that also need not be harsh.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. a preparation method for load type non-metallocene catalyst, comprises the following steps:

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

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

The first mixed serum described in convection drying, the step of acquisition complex carrier;

The chemical processing agent that is selected from IVB family metallic compound is reacted with described complex carrier, obtain the step of modifying complex carrier;

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

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

2. according to the preparation method described in 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, refractory oxide or the infusibility composite oxides of IVAHuo IVB family metal, clay, molecular sieve, mica, polynite, one or more in wilkinite and diatomite, be preferably selected from partial cross-linked styrene polymer, silicon-dioxide, aluminum oxide, magnesium oxide, oxidation sial, oxidation magnalium, titanium dioxide, one or more in molecular sieve and polynite, more preferably be selected from silicon-dioxide.

3. according to the preparation method described in 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 alkyl alkoxy magnesium, be preferably selected from one or more in magnesium halide, more preferably magnesium chloride.

4. according to the preparation method described in 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 _6-12one or more in aromatic hydrocarbon, ester and ether, are preferably selected from C _5-12alkane, C _5-12naphthenic hydrocarbon, C _6-12one or more in aromatic hydrocarbon and tetrahydrofuran (THF), are most preferably selected from one or more in tetrahydrofuran (THF) and hexane, and described alcohol is selected from C _1-30fatty alcohol, C _6-30aromatic alcohol and C _4-30one or more in alicyclic ring alcohol, wherein said alcohol is optionally selected from halogen atom or C _1-6the substituting group of alkoxyl group replaces, and described alcohol is preferably selected from C _1-30one or more in aliphatic monobasic alcohol, are more preferably selected from one or more in ethanol, butanols and 2-Ethylhexyl Alcohol, and described the second solvent is selected from C _6-12aromatic hydrocarbon, halo C _6-12aromatic hydrocarbon, halo C _1-10one or more in alkane, ester and ether, be preferably selected from one or more in toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and tetrahydrofuran (THF), more preferably C _6-12one or more in aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).

5. according to the preparation method described in 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 and there are the compound (A) of following chemical structural formula and one or more in compound (B):

More preferably be selected from one or more in to compound (A-4) and compound (B-1) to compound (B-4) of the 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, containing seleno group, phosphorus-containing groups or cyano group, 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, containing seleno group or phosphorus-containing groups, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

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, containing seleno group or phosphorus-containing groups, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, 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 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 nitrogen, hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R ⁵during for oxy radical, sulfur-containing group, nitrogen-containing group, 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 is further preferably selected from one or more in the compound with following chemical structural formula:

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

6. according to the preparation method described in 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 is selected from hydroxyl ,-OR ³⁴with-T-OR ³⁴;

Be selected from-SR of described sulfur-containing group ³⁵,-T-SR ³⁵,-S (O) R ³⁶or-T-SO ₂r ³⁷;

Described containing be selected from-SeR of seleno group 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 contains 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;

Be selected from-SiR of described silicon-containing group ⁴²r ⁴³r ⁴⁴or-T-SiR ⁴⁵;

Described be selected from-GeR of germanic group ⁴⁶r ⁴⁷r ⁴⁸or-T-GeR ⁴⁹;

Described containing be selected from-SnR of tin group 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 preparation method described in 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:

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 Dao XI family atoms metal, preferably 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, containing aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or containing tin group, a plurality of X can be identical, also can be different, can also be each other in key or Cheng Huan;

Y is selected from Sauerstoffatom, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, 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 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

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

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

8. according to the preparation method described in aforementioned either side, it is characterized in that,

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

Described oxy radical is selected from hydroxyl ,-OR ³⁴with-T-OR ³⁴;

Described boron-containing group is selected from BF ₄ ^-, (C ₆f ₅) ₄b ^-or (R ⁴⁰bAr ₃) ^-;

Describedly be selected from aluminum alkyls, AlPh containing aluminium base group ₄ ^-, AlF ₄ ^-, AlCl ₄ ^-, AlBr ₄ ^-, AlI ₄ ^-or R ⁴¹alAr ₃ ^-;

Described containing be selected from-SnR of tin group 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 preparation method described in aforementioned either side, it is characterized in that, take the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene title complex is 1: 0.01-1, preferably 1: 0.04-0.4, more preferably 1: 0.08-0.2, take the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene part is 1: 0.0001-1, preferably 1: 0.0002-0.4, more preferably 1: 0.0008-0.2, further preferably 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 described magnesium compound of magnesium compound solid and the mass ratio of described porous support is 1: 0.1-20, preferably 1: 0.5-10, more preferably 1: 1-5, the mol ratio of the described chemical processing agent that the described magnesium compound Yu Yi IVB family metallic element of Mg element of take is counted is 1: 0.01-1, preferably 1: 0.01-0.50, more preferably 1: 0.10-0.30, and take the described magnesium compound of Mg element and the mol ratio of described alcohol is 1: 0.02～4.00, preferably 1: 0.05～3.00, more preferably 1: 0.10～2.50.

10. according to the preparation method described in 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, metal alkyl halides HeIVB family of IVB family metal alkoxide halogenide, be preferably selected from one or more in IVB family metal halide, be more preferably selected from TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄and HfBr ₄in one or more, be most preferably selected from TiCl ₄and ZrCl ₄in one or more.

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

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

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

14. 1 kinds of load type non-metallocene catalysts, it is to be manufactured by the preparation method according to aforementioned either side.

15. 1 kinds of alkene homopolymerization/copolymerization process, it is characterized in that, take according to the load type non-metallocene catalyst described in aspect 14 is Primary Catalysts, take that to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt be promotor, make alkene homopolymerization or it is poly-.

16. 1 kinds of alkene homopolymerization/copolymerization process, is characterized in that, comprise the following steps:

According to the preparation method described in aforementioned either side, manufacture load type non-metallocene catalyst, and

Take described load type non-metallocene catalyst as Primary Catalysts, take that to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt be 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 and at catalysis in olefine polymerization, obtain the performance of polyolefin product.

Adopt method for preparing catalyst provided by the invention, because catalyzer prepares by Nonmetallocene part YuIVB family's chemical processing agent reaction in－situ and then two steps of load non-metallocene metal complexes, in catalyzer, the controlled leeway of molar ratio of the constituent content of active metal and conventional active metal and Nonmetallocene title complex is large, thereby effectively controls catalyst activity and polymer performance.

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

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

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 contributes to improve polymer stacks density, the molecular weight distribution that narrows, improves 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

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

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

The preparation method who the present invention relates to a kind of load type non-metallocene catalyst, comprises the following steps: magnesium compound is dissolved in the first solvent under the existence of alcohol, obtains the step of magnesium compound solution; Optionally porous support, the described magnesium compound solution of process thermal activation treatment are contacted with Nonmetallocene part, obtain the step of the first mixed serum; The first mixed serum described in convection drying, the step of acquisition complex carrier; The chemical processing agent that is selected from IVB family metallic compound is reacted with described complex carrier, obtain the step of modifying complex carrier; Nonmetallocene title complex is contacted under the existence of the second solvent with described modification complex carrier, obtain the step of the second mixed serum; With the second mixed serum described in convection drying, obtain the step of described load type non-metallocene catalyst.

Below described magnesium compound is specifically described.

According to the present invention, term " magnesium compound " is used the common concept in this area, refers to the conventional organic or inorganic solid water-free magnesium-containing compound using of carrier as 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 preferably 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 preferably 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 preferably 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 separately a kind of, also can multiple mixing use, not special restriction.

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

To obtaining the step of described magnesium compound solution, be specifically described below.

According to this step, make magnesium compound under the existence of alcohol, be dissolved in suitable solvent (hereinafter referred to as for dissolving solvent or first solvent of 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 preferably hexane, heptane and decane, most preferably hexane.

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

As described halo C _1-10alkane, 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, 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, such as enumerating toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene.

As described halo C _6-12aromatic hydrocarbon, 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 Nonmetallocene part hereinafter described.

These solvents can be used separately a kind of, also can use with the multiple mixing of ratio arbitrarily.

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 (preferred C _1-30aliphatic monobasic alcohol), C _6-30aromatic alcohol (preferred C _6-30aromatic 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 optionally selected from halogen atom or C _1-6the substituting group of alkoxyl group replaces.

As described C _1-30fatty alcohol, 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 preferably hexalin and methyl-cyclohexanol.

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

The described alcohol replacing 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 separately a kind of, also can multiple mixing use.When the form with multiple mixing is used, the ratio between any two kinds of alcohol in described alcohol mixture can be to determine arbitrarily, is not particularly limited.

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

To the preparation time of described magnesium compound solution (being the dissolution time of described magnesium compound), there is no particular limitation, but be generally 0.5～24h, preferably 4～24h.In this preparation process, can utilize and stir the dissolving that promotes described magnesium compound.This stirring can adopt any form, such as stirring rake (rotating speed is generally 10～1000 revs/min) etc.As required, sometimes can promote to dissolve by suitable heating (but top temperature must 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, in structure, do not contain the cyclopentadienyl or derivatives thereofs such as luxuriant ring, fluorenes ring or indenes ring, and when with promotor (such as hereinafter described those) combination, can demonstrate the organometallics (therefore described Nonmetallocene title complex is also sometimes referred to as non-metallocene olefin polymerization title complex) of olefinic polymerization catalysis activity.This compound comprises central metal atom and at least one polydentate ligand of being combined with coordinate bond with described central metal atom (preferably tridentate ligand or more polydentate ligand), 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 the contained IVB family atoms metal generation coordination reaction of IVB family metallic compound of using as chemical processing agent in its contained atom for coordination (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 Yi Gai IVB family atoms metal.

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

At one more specifically in embodiment, described Nonmetallocene part is selected from the 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;

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

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyano group (CN), such as can enumerate-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 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, or 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 nitrogen, hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups.Work as R ⁵during for oxy radical, sulfur-containing group, nitrogen-containing group, 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, such as R ²¹with group Z, or 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 optionally selected from C by one or more ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀the substituting group of alkyl and safing function group replaces.

In the context of the present invention,

Described halogen is selected from F, Cl, Br or I.Described nitrogen-containing group is selected from -NR ²³r ²⁴,-T-NR ²³r ²⁴or-N (O) R ²⁵r ²⁶.Described phosphorus-containing groups is selected from -PR ²⁸r ²⁹,-P (O) R ³⁰r ³¹or-P (O) R ³²(OR ³³).Described oxy radical is selected from hydroxyl ,-OR ³⁴with-T-OR ³⁴.Be selected from-SR of described sulfur-containing group ³⁵,-T-SR ³⁵,-S (O) R ³⁶or-T-SO ₂r ³⁷.Described containing be selected from-SeR of seleno group ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹or-T-Se (O) R ³⁹.Described group T is selected from C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group.Described R ³⁷be selected from hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group.

In the context of the present invention, described C ₁-C ₃₀alkyl is selected from C ₁-C ₃₀alkyl (preferred C ₁-C ₆alkyl, 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 contains 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 to its combination, described C ₁-C ₃₀alkyl refers to C sometimes ₁-C ₃₀hydrocarbon two bases (divalent group, or be called C 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, refer to these substituting groups to aforementioned for coordination group (refer to aforementioned group A, D, E, F, Y and Z, or also optionally comprise R ⁵) there is no 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 being subject to the impact of 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, 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, such as enumerating, be selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, contain tin group, C ₁-C ₁₀ester group and nitro (NO ₂) at least one 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) with the coordination ability of described IVB family atoms metal lower than described A, D, E, F, Y and Z group, and do not replace the existing coordination of these groups and described IVB family atoms metal.

In the context of the present invention, be selected from-SiR of described silicon-containing group ⁴²r ⁴³r ⁴⁴or-T-SiR ⁴⁵; Described be selected from-GeR of germanic group ⁴⁶r ⁴⁷r ⁴⁸or-T-GeR ⁴⁹; Described containing be selected from-SnR of tin group ⁵⁰r ⁵¹r ⁵²,-T-SnR ⁵³or-T-Sn (O) R ⁵⁴; And 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 is further preferably selected from following compound:

Described Nonmetallocene part is more preferably selected from following compound:

These Nonmetallocene parts can be used separately a kind of, or 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 manufactured 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 specifically described.

According to the present invention, as described porous support, such as can enumerate this area when manufacturing 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 be less than 100%) styrene polymer.

A preferred embodiment according to the present invention, preferably on the surface of described Porous-Organic solid with any one or multiple active function groups such as being 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 hydrazide group, preferred at least one in carboxyl and hydroxyl wherein.

According to an embodiment of the invention, before use described Porous-Organic solid is carried out to thermal activation treatment.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under inert atmosphere, described Porous-Organic solid being carried out to heat treated.Here said inert atmosphere refer in gas, only contain 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.Due to the poor heat resistance of Porous-Organic solid, so this thermal activation process is not to destroy the structure of described Porous-Organic solid itself and to basic composition is prerequisite.Usually, the temperature of this thermal activation is 50～400 ℃, preferably 100～250 ℃, and the thermal activation time is 1～24h, and preferred 2～12h.After thermal activation treatment, described Porous-Organic solid need to save backup in malleation under inert atmosphere.

As described inorganic porous solid, such as enumerating the refractory oxide (such as silicon-dioxide (being called again silicon oxide or silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium white or Thorotrast etc.) of periodic table of elements IIA, IIIA, IVAHuo IVB family metal, or 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 being generated by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound, such as the silica gel being obtained by silicon tetrachloride pyrohydrolysis, or the aluminum oxide being obtained by 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 manufactured by ordinary method, or can be the commerical prod that can buy arbitrarily, such as enumerating Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245 and the Aerosil812 of Grace company, the ES70 of Ineos company, ES70X, ES70Y, ES70W, ES757, EP10X and EP11, and the CS-2133 of Pq Corp. and MS-3040.

A 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 to thermal activation treatment.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under inert atmosphere, described inorganic porous solid being carried out to heat treated.Here said inert atmosphere refer in gas, only contain 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 preferably 400～700 ℃, most preferably 400～650 ℃, heat-up time is such as being 0.5～24h, preferably 2～12h, most preferably 4～8h.After thermal activation treatment, described inorganic porous solid need to save backup in malleation under inert atmosphere.

According to the present invention, to the surface-area of described porous support, there is no particular limitation, but be generally 10～1000m ²/ g (BET method mensuration), preferably 100～600m ²/ g; The pore volume of this porous support (determination of nitrogen adsorption) is generally 0.1～4cm ³/ g, preferably 0.2～2cm ³/ g, and its median size (laser particle analyzer mensuration) preferably 1～500 μ m, 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 manufacturing described the first mixed serum, 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., there is no particular limitation, such as enumerating, the described optional porous support through thermal activation treatment is first mixed with described magnesium compound solution, and then add wherein the scheme of described Nonmetallocene part; Make described optional scheme of simultaneously mixing through porous support, described magnesium compound solution and the described Nonmetallocene part of thermal activation treatment; Or described Nonmetallocene part and described magnesium compound are dissolved in foregoing the first solvent, manufacture thus the mixing solutions (hereinafter sometimes also referred to as magnesium compound solution) of magnesium compound and Nonmetallocene part, and then make described optional scheme of mixing with described mixing solutions through the porous support of thermal activation treatment etc.

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

Now, the first mixed serum obtaining 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 the airtight standing of certain hour (2～48h, preferably 4～24h, most preferably 6～18h) 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.

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

Below described chemical processing agent is specifically described.

According to the present invention, YiIVB family metallic compound is as described chemical processing agent.

As described IVB family metallic compound, such as can enumerate be selected from IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, metal alkyl halides HeIVB family of IVB family metal alkoxide halid at least one.

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 enumerating the compound of 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 periodic table of elements ZhongIVB family metal, 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, 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 separately a kind of, or are used in combination multiple with ratio arbitrarily.

According to the present invention, the chemical processing agent that makes to be selected from described IVB family metallic compound reacts (chemical treatment reaction) with described complex carrier, obtain and modify complex carrier.

When described chemical processing agent is liquid state at normal temperatures, can use described chemical processing agent by directly dripping the mode of the described chemical processing agent of predetermined amount in the reaction object (such as aforesaid complex carrier) to needing to utilize this chemical processing agent to process.When described chemical processing agent is while being solid-state at normal temperatures, for measure with easy to operate for the purpose of, preferably with the form of solution, use described chemical processing agent.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, be not particularly limited.

When the solution of the described chemical processing agent of preparation, to the solvent that now used, 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 preferably pentane, hexane, decane, hexanaphthene and toluene, most preferably hexane and toluene.

These solvents can be used separately a kind of, or are used in combination multiple with ratio arbitrarily.

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

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

As carrying out described chemically treated method, such as enumerating, in the situation that chemical processing agent is solid-state (such as zirconium tetrachloride), first the solution of preparing described chemical processing agent, then to the described solution of the described chemical processing agent that adds in pending reaction object (such as aforesaid complex carrier) (preferably dripping) to contain predetermined amount, to carry out chemical treatment reaction.In the situation that chemical processing agent is liquid (such as titanium tetrachloride), can directly the described chemical processing agent of predetermined amount be added in (preferably dripping) pending reaction object (such as aforesaid complex carrier), to carry out chemical treatment reaction, or after this chemical processing agent is prepared into solution, to the described solution of the described chemical processing agent that adds in pending reaction object (such as aforesaid complex carrier) (preferably dripping) to contain predetermined amount, to carry out chemical treatment reaction.

Generally speaking, under the temperature of reaction of-30～60 ℃ (preferably-20～30 ℃), make described chemical treatment reaction (if desired by stirring) carry out 0.5～24 hour, preferably 1～8 hour, more preferably 2～6 hours.

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

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

Described being dried can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or vacuum, and heat drying method, most preferably heat drying method under vacuum under preferred rare gas element desiccating method or vacuum.Described dry temperature range 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 dry, obtained processing product is separated completely, and then used this processing product to carry out next step reaction or processing.

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

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

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

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

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

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

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, containing aluminium base group, phosphorus-containing groups, silicon-containing group, germanic group or containing tin group, a plurality of X can be identical, also can be different, 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;

→ 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 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, or 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

In the context of the present invention, described halogen is selected from F, Cl, Br or I.Described nitrogen-containing group is selected from -NR ²³r ²⁴,-T-NR ²³r ²⁴or-N (O) R ²⁵r ²⁶.Described phosphorus-containing groups is selected from -PR ²⁸r ²⁹,-P (O) R ³⁰r ³¹or-P (O) R ³²(OR ³³).Described oxy radical is selected from hydroxyl ,-OR ³⁴with-T-OR ³⁴.Be selected from-SR of described sulfur-containing group ³⁵,-T-SR ³⁵,-S (O) R ³⁶or-T-SO ₂r ³⁷.Described containing be selected from-SeR of seleno group ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹or-T-Se (O) R ³⁹.Described group T is selected from C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group.Described R ³⁷be selected from hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group.

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, refer to these substituting groups to aforementioned for coordination group (refer to aforementioned group A, D, E, F, Y and Z, or also optionally comprise radicals R ⁵) there is no 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 being subject to the impact of 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, 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, such as enumerating, be selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, contain tin group, C ₁-C ₁₀ester group or nitro (NO ₂) at least one 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) with the coordination ability of described central metal atom M lower than described A, D, E, F, Y and Z group, and do 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 be selected from aluminum alkyls, AlPh containing aluminium base group ₄ ^-, AlF ₄ ^-, AlCl ₄ ^-, AlBr ₄ ^-, AlI ₄ ^-or R ⁴¹alAr ₃ ^-; Be selected from-SiR of described silicon-containing group ⁴²r ⁴³r ⁴⁴or-T-SiR ⁴⁵; Described be selected from-GeR of germanic group ⁴⁶r ⁴⁷r ⁴⁸or-T-GeR ⁴⁹; Described containing be selected from-SnR of tin group 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 is further preferably selected from following compound:

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

These Nonmetallocene title complexs can be used separately a kind of, or are used in combination multiple with ratio arbitrarily.

According to the present invention, the described polydentate ligand in 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 manufactured 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 under the existence of the second solvent, contact (contact reacts) with described Nonmetallocene title complex, can obtain described the second mixed serum.

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

In addition, in order to manufacture described the second mixed serum, such as can be at normal temperature to the temperature lower than the boiling point of used any solvent, described modification complex carrier and the described Nonmetallocene title complex contact reacts (if desired by stirring) under described the second solvent exists is carried out 0.5～24 hour, preferably 1～8 hour, more preferably 2～6 hours.

Now, the second mixed serum obtaining 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 the airtight standing of certain hour (2～48h, preferably 4～24h, most preferably 6～18h) afterwards in preparation.

According to the present invention, when manufacturing described the second mixed serum, to described the second solvent (be sometimes referred to as below and dissolve Nonmetallocene title complex solvent), there is no particular limitation, as long as it 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 _1-10one or more in alkane, ester and ether.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).

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

According to the present invention, to the consumption of described the second solvent without any restriction, so long as be enough to realize the amount that described modification complex carrier fully contacts with described Nonmetallocene title complex.Such as, 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 be sometimes not limited to this.

Then,, by 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.

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

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

Below the described chemical processing agent that helps is specifically described.

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 following general formula (I): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in 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 within the scope of 1-50, preferably the arbitrary integer in 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 separately a kind of, or are used in combination multiple with ratio arbitrarily.

As described aluminum alkyls, such as enumerating the compound shown in 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 preferably trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.

These aluminum alkylss can be used separately a kind of, or 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 to the ratio of each component in this mixture, there is no particular limitation, can select arbitrarily as required.

According to the present invention, described in to help chemical processing agent be generally to use with the form of solution.When helping the solution of chemical processing agent described in preparation, to the solvent that now used, there is no particular limitation, as long as it can dissolve this and help chemical processing agent.

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

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

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

As the method for carrying out described pre-treatment step, such as enumerating, first described in preparing, help the solution of chemical processing agent, then to intend with described in help in the pretreated described modification complex carrier of chemical processing agent to be metered into and help chemical treatment agent solution (wherein contain predetermined amount described in help chemical processing agent) described in (preferably dripping), or to the described chemical treatment agent solution amount of falling into a trap that helps, add described modification complex carrier, form thus reaction mixture.Now, temperature of reaction is generally-40～60 ℃, and preferably-30～30 ℃, the reaction times is generally 1～8h, preferably 2～6h, most preferably 3～4h (if desired by stirring).Then, by filtration, washing and optionally drying, from this reaction mixture, isolate pre-treatment product.

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

According to the present invention, described filtration, washing and dryly can adopt ordinary method to carry out, wherein washer solvent can adopt with dissolve described in identical solvent used while helping chemical processing agent.As required, this washing is generally carried out 1～8 time, and preferably 2～6 times, most preferably 2～4 times.Described being dried can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or vacuum, and heat drying method, most preferably heat drying method under vacuum under preferred rare gas element desiccating method or vacuum.Described dry temperature range 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, make to reach 1 in the described magnesium compound (solid) of Mg element and the mol ratio of described Nonmetallocene title complex: 0.01-1, preferably 1: 0.04-0.4, more preferably 1: 0.08-0.2.

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

According to the present invention, as described for dissolving the solvent of described magnesium compound or the consumption of the first solvent, make described magnesium compound (solid) and the ratio of described solvent reach 1mol: 75～400ml, preferably 1mol: 150～300ml, more preferably 1mol: 200～250ml.

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

According to the present invention, consumption as described chemical processing agent, make to reach 1 in the mol ratio of the described chemical processing agent of described magnesium compound (solid) Yu Yi IVB family's metal (such as Ti) element meter of Mg element: 0.01-1, preferably 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, make in the described magnesium compound (solid) of Mg element with to help the mol ratio of chemical processing agent to reach 1 described in Al element: 0-1.0, preferably 1: 0-0.5, more preferably 1: 0.1-0.5.

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

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

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

In a further embodiment, the present invention relates to a kind of alkene homopolymerization/copolymerization process, wherein using 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 content particularly pointing out below, other contents of not explaining (such as the addition manner of reactor, alkene consumption, catalyzer and alkene for polymerization etc.), can directly be suitable for conventional known those in this area, not special restriction, at this, the description thereof will be omitted.

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

Primary Catalysts and promotor can be first to add Primary Catalysts to the mode that adds in polymerization reaction system, and then add promotor, or first add promotor, and then add Primary Catalysts, or both add after first contacting mixing together, or add respectively simultaneously.Primary Catalysts and promotor are added respectively and fashionablely both can in same reinforced pipeline, be added successively, also can in the reinforced pipeline of multichannel, add successively, and both add respectively simultaneously and fashionablely should select the multichannel pipeline that feeds in raw material.For continous way polyreaction, preferably the reinforced pipeline of multichannel adds simultaneously continuously, and for intermittence type polymerization reaction, preferably both add together after first mixing in same reinforced pipeline, or in same reinforced pipeline, first add promotor, and then add Primary Catalysts.

According to the present invention, to the reactive mode of described alkene homopolymerization/copolymerization process, there is no particular limitation, 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, 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, or the 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 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 following general formula (I-1): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in 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 within the scope of 1-50, preferably the arbitrary integer in 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.

Al(R) ₃

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 preferably trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum and triisobutyl aluminium, further preferably triethyl aluminum and triisobutyl aluminium, and triethyl aluminum most preferably.

As described haloalkyl aluminium, such as enumerating the compound shown in 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, preferably 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), 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), 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 preferably 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 preferably chlorodiethyl aluminium, ethyl aluminum dichloride and a chlorine di-n-hexyl aluminium, and aluminium diethyl monochloride most preferably.

These haloalkyl aluminium can be used separately a kind of, or 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 separately a kind of, also can be as required with ratio arbitrarily, be used in combination multiple aforesaid promotor, not special restriction.

According to the present invention, according to the difference of the reactive mode of described alkene homopolymerization/copolymerization process (such as slurry polymerization), sometimes need to use polymerization solvent.

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 separately a kind of with solvent, or 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 be sometimes not limited to this.According to the present invention, polymeric reaction temperature is generally-40 ℃～200 ℃, and preferably 10 ℃～100 ℃, more preferably 40 ℃～95 ℃, but be sometimes 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 under the condition of hydrogen, carry out not having.In the situation that existing, the dividing potential drop of hydrogen can be 0.01%～99% of described polymerization pressure, preferably 0.01%～50%, but be sometimes not limited to this.

According to the present invention, when carrying out described alkene homopolymerization/copolymerization process, in the described promotor of aluminium or boron and the mol ratio of described load type non-metallocene catalyst in described central metal atom, be generally 1～1000: 1, preferably 10～500: 1, more preferably 15～300: 1, but be sometimes 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 with reference to CNS GB 1636-79, carry out.

The content of load type non-metallocene catalyst ZhongIVB family metal (such as Ti) and Mg element adopts ICP-AES method to measure, 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 reactor is filtered and is dried, then weigh the quality of this polymerisate, with this polymerisate quality, divided by the ratio of the quality of load type non-metallocene catalyst used, represent the polymerization activity (unit is kg polymkeric substance/g catalyzer or kg polymkeric substance/gCat) of this catalyzer.

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 with 1,2,4-trichlorobenzene, for solvent, 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, 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 according to following formula, calculate the viscosity-average molecular weight Mv of described polymkeric substance.

Mv＝5.37×10 ⁴×[η] ^1.37

Wherein, η is limiting viscosity.

Embodiment 1

Magnesium compound adopts Magnesium Chloride Anhydrous, and 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, first silica gel is continued to 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 Nonmetallocene title complex adopts structure to be compound.

Take 5 grams of magnesium compounds, join after the first solvent, add again alcohol and Nonmetallocene part, completely dissolve and obtain magnesium compound solution at normal temperatures, then add porous support, stir after 2 hours, obtain the first mixed serum, then homogeneous heating to 90 ℃, directly vacuumizes dryly, obtains complex carrier.

The complex carrier making is joined in 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, finally at 60 ℃, vacuumize dryly, obtain modifying complex carrier.

At room temperature, Nonmetallocene title complex is joined in the second solvent, then add modification complex carrier, stir 4 hours, then after airtight standing 12 hours, directly vacuumize dryly, obtain load type non-metallocene catalyst.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 2; In Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.08; With alcohol mole proportioning be 1: 2; With the proportioning of the first solvent hexane be 1mol: 210ml; With 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 have following change:

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

; modification complex carrier is joined in hexane solvent; slowly drip again and help chemical processing agent triethyl aluminum (concentration is 0.88mol/L; hexane solution); at 60 ℃, stir after 2 hours and filter, hexane washing 3 times, each 60ml; finally at 60 ℃, vacuumize dryly, obtain pretreated modification complex carrier.Wherein magnesium compound is 1: 0.2 with helping 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 have following change:

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

; modification complex carrier is joined in toluene solvant; slowly drip again and help chemical processing agent methylaluminoxane (concentration is 10wt%; toluene solution); at 60 ℃, stir after 2 hours and filter, toluene wash 3 times, each 60ml; finally at 100 ℃, vacuumize dryly, obtain pretreated modification complex carrier.Wherein magnesium compound is 1: 0.4 with helping 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 have following change:

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 Nonmetallocene part adopts porous support is changed into 955 of Grace company, under 400 ℃, nitrogen atmosphere, continues roasting 8h and thermal activation.Chemical processing agent changes zirconium tetrachloride (ZrCl into ₄).

Nonmetallocene title complex adopts the second solvent changes toluene into, the first mixed serum change at 100 ℃, directly vacuumize dry.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 1; In Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.04; With alcohol mole proportioning be 1: 1; With the proportioning of the first solvent be 1mol: 150ml; With 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 have following change:

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 Nonmetallocene part adopts porous support adopts aluminium sesquioxide.Aluminium sesquioxide is continued under 700 ℃, nitrogen atmosphere to roasting 6h.Chemical processing agent changes titanium tetrabromide (TiBr into ₄),

Nonmetallocene title complex adopts the first mixed serum change at 110 ℃, directly vacuumize dry.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 5; In Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.2; With alcohol mole proportioning be 1: 0.7; With the proportioning of the first solvent be 1mol: 280ml; With 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 have following change:

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

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 change at 120 ℃, directly vacuumize dry.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 10; In Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.05; With alcohol mole proportioning be 1: 0.7; With the proportioning of the first solvent be 1mol: 200ml; With 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 have following change:

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 Nonmetallocene part adopts porous support adopting montmorillonite.Polynite is continued under 400 ℃, nitrogen atmosphere to roasting 8h.The chemical processing agent of IVB family metallic compound is changed into tetra-n-butyl titanium (Ti (C ₄h ₉) ₄), Nonmetallocene title complex adopts the first mixed serum change at 130 ℃, directly vacuumize dry.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 3; In Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.4; With alcohol mole proportioning be 1: 1.5; With 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 have following change:

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 to dry under 85 ℃, nitrogen atmosphere 12h.Nonmetallocene part adopts 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 Mg element, the mol ratio of magnesium compound and Nonmetallocene part is 1: 0.01; With alcohol mole proportioning be 1: 2.5; With the proportioning of the first solvent hexane be 1mol: 210ml; With 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 have following change:

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 Nonmetallocene part adopts porous support adopts diatomite.Diatomite is continued under 500 ℃, nitrogen atmosphere to roasting 8h.The chemical processing agent of IVB family metallic compound is changed into purity titanium tetraethoxide (Ti (OCH ₃cH ₂) ₄), Nonmetallocene title complex adopts load type non-metallocene catalyst is designated as CAT-9.

Embodiment 10

Substantially the same manner as Example 1, but have following change: 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 Nonmetallocene part adopts porous support adopts titanium dioxide.Titanium dioxide is continued under 300 ℃, nitrogen atmosphere to roasting 6h.

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 have following change:

In load type non-metallocene catalyst preparation process, do not add Nonmetallocene part;

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

Reference example B

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

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

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

Reference example C

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

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 have following change:

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 have following change:

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

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

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.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 20mg load type non-metallocene catalyst and catalyst mixture, then add hydrogen to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.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.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 20mg load type non-metallocene catalyst and catalyst mixture, the disposable hexene-1 comonomer 50g that adds, add again hydrogen to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.

Preparing 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.First 2.5 liters of hexanes are joined in 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, finally continues to pass into ethene and makes polymerization stagnation pressure constant in 0.5MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 2.

From table 1, the molecular weight distribution that the load type non-metallocene catalyst polymerization of preparing by method provided by the invention obtains is narrower, those skilled in the art know, generally adopt the molecular weight of polyethylene distribution that Ziegler-Natta catalyst polymerization obtains to be greater than 5.

Known by sequence number in table 11 and 3,5 and 7,8 and 10 test-results data, increase the consumption of promotor, improve promotor and catalyst activity metal molar than time, impact active on polymerization catalyst and polymer stacks density is not remarkable.It can be said that brightly, adopt load type non-metallocene catalyst prepared by method provided by the invention 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 contrast table 1,5 and 6,8 and 9 test-results data are known, after copolymerization, catalyst activity has increase by a relatively large margin, thereby the load type non-metallocene catalyst that explanation adopts method provided by the invention to prepare has comparatively significant comonomer effect.

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

By sequence number 1 in contrast table 1 and comparative example sequence number 21 and 22, and in table 2, the test-results data of sequence number 1 and comparative example 10 and 11 are known, the proportioning of magnesium compound and porous support in reduction and 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 contributes to improve polymer stacks density, the molecular weight distribution that narrows, improves 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 the specific embodiment of the present invention is had been described in detail above, it is pointed out that protection scope of the present invention is not subject to the restriction of these embodiments, but determined by claims of appendix in conjunction with the embodiments.Those skilled in the art can carry out suitable change to these embodiments in the scope that does not depart from technological thought of the present invention and purport, and within these embodiments after changing are obviously also included within protection scope of the present invention.

Claims

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

Wherein said preparation method is optionally also included in and makes before described Nonmetallocene title complex contacts with described modification complex carrier, by the step of modifying complex carrier described in chemical processing agent pre-treatment that helps that is selected from 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, refractory oxide or the infusibility composite oxides of IVAHuo IVB family metal, clay, molecular sieve, mica, polynite, one or more in wilkinite and diatomite.

3. according to preparation method claimed in claim 2, it is characterized in that, described porous support is selected from silicon-dioxide.

4. 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 alkyl alkoxy magnesium.

5. according to preparation method claimed in claim 4, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide.

6. 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 _6-12one or more in aromatic hydrocarbon, ester and ether, described alcohol is selected from C _1-30fatty alcohol, C _6-30aromatic alcohol and C _4-30one or more in alicyclic ring alcohol, wherein said alcohol is optionally selected from halogen atom or C _1-6the substituting group of alkoxyl group replaces, and described the second solvent is selected from C _6-12aromatic hydrocarbon, halo C _6-12aromatic hydrocarbon, halo C _1-10one or more in alkane, ester and ether.

7. according to preparation method claimed in claim 6, it is characterized in that, described the first solvent is selected from one or more in tetrahydrofuran (THF) and hexane, and described alcohol is selected from one or more in ethanol, butanols and 2-Ethylhexyl Alcohol, and described the second solvent is selected from C _6-12one or more in aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).

8. 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,

In above chemical structural formula,

Q is 0 or 1;

D is 0 or 1;

D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C ₁-C ₃₀alkyl, sulfuryl or sulfoxide 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 ³be selected from independently of one another hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group, R ²²to R ³³and R ³⁹be selected from independently of one another hydrogen, C ₁-C ₃₀the C of alkyl or replacement ₁-C ₃₀alkyl, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan,

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

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

Described oxy radical is selected from hydroxyl ,-OR ³⁴with-T-OR ³⁴;

Described group T is selected from C ₁-C ₃₀the C of alkyl or replacement ₁-C ₃₀alkyl;

Described R ³⁷be selected from hydrogen, C ₁-C ₃₀the C of alkyl or replacement ₁-C ₃₀alkyl;

Described C ₁-C ₃₀alkyl is selected from C ₁-C ₃₀alkyl, C ₇-C ₃₀alkaryl, C ₇-C ₃₀aralkyl, 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 contains 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;

Wherein, be selected from-SiR of described silicon-containing group ⁴²r ⁴³r ⁴⁴or-T-SiR ⁴⁵; Described be selected from-GeR of germanic group ⁴⁶r ⁴⁷r ⁴⁸or-T-GeR ⁴⁹; Described containing be selected from-SnR of tin group ⁵⁰r ⁵¹r ⁵²,-T-SnR ⁵³or-T-Sn (O) R ⁵⁴;

Described R ³⁴to R ³⁶, R ³⁸and R ⁴²to R ⁵⁴be selected from independently of one another hydrogen, aforementioned C ₁-C ₃₀the C of alkyl or aforementioned replacement ₁-C ₃₀alkyl, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and

Described group T ditto defines.

9. according to preparation method claimed in claim 8, it is characterized in that, described Nonmetallocene part is selected from has the compound (A) of following chemical structural formula and one or more in compound (B),

In above all chemical structural formulas,

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

10. according to preparation method claimed in claim 9, it is characterized in that, described Nonmetallocene part is selected from one or more in to compound (A-4) and compound (B-1) to compound (B-4) of the compound (A-1) with following chemical structural formula:

In above all chemical structural formulas,

R ⁴, R ⁶to R ²¹be 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; And

R ⁵be selected from lone-pair electron on nitrogen, hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R ⁵during for oxy radical, sulfur-containing group, nitrogen-containing group, 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 center IVB family atoms metal.

11. 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:

12. according to the preparation method described in claim 11, it is characterized in that, described Nonmetallocene part is selected from one or more in the compound with following chemical structural formula,

13. according to preparation method claimed in claim 1, it is characterized in that, take the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene title complex is 1: 0.01-1, take the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene part is 1: 0.0001-1, the ratio of described magnesium compound and described the first solvent is 1mol: 75～400ml, take the described magnesium compound of magnesium compound solid and the mass ratio of described porous support is 1: 0.1-20, the mol ratio of the described chemical processing agent that the described magnesium compound Yu Yi IVB family metallic element of Mg element of take is counted is 1: 0.01-1, take the described magnesium compound of Mg element and the mol ratio of described alcohol is 1: 0.02～4.00, and in the described magnesium compound of Mg element with take Al element described in help the mol ratio of chemical processing agent as 1: 0-1.0.

14. 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, metal alkyl halides HeIVB family of IVB family metal alkoxide halogenide.

15. according to the preparation method described in claim 14, it is characterized in that, described IVB family metallic compound is selected from one or more in IVB family metal halide.

16. 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:

In above chemical structural formula,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from periodic table of elements III-th family Dao XI family atoms metal;

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

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

Described oxy radical is selected from hydroxyl ,-OR ³⁴with-T-OR ³⁴;

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

Wherein, described boron-containing group is selected from BF ₄ ^-, (C ₆f ₅) ₄b ^-or (R ⁴⁰bAr ₃) ^-;

Described Ar represents C ₆-C ₃₀aryl, and

R ³⁴to R ³⁶, R ³⁸and R ⁴⁰to R ⁵⁴be selected from independently of one another hydrogen, aforementioned C ₁-C ₃₀the C of alkyl or aforementioned replacement ₁-C ₃₀alkyl, wherein these groups can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan,

And described group T ditto defines.

17. according to the preparation method described in claim 16, it is characterized in that, described Nonmetallocene title complex is selected from has the compound (A) of following chemical structural formula and one or more in compound (B):

In above all chemical structural formulas,

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

18. according to the preparation method described in claim 17, it is characterized in that, described Nonmetallocene title complex is selected from one or more in to compound (A-4) and compound (B-1) to compound (B-4) of the compound (A-1) with following chemical structural formula:

In above all chemical structural formulas,

R ⁴, R ⁶to R ²¹be 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, and

19. 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:

20. according to the preparation method described in claim 19, it is characterized in that, described Nonmetallocene title complex is selected from one or more in the compound with following chemical structural formula:

21. 1 kinds of load type non-metallocene catalysts, it is to be manufactured by the preparation method according to described in claim 1-20 any one.

22. 1 kinds of alkene homopolymerization/copolymerization process, it is characterized in that, take according to the load type non-metallocene catalyst described in claim 21 is Primary Catalysts, take that to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt be promotor, make alkene homopolymerization or copolymerization.