CN102964483B

CN102964483B - Supported non-metallocene catalyst, preparation method and application

Info

Publication number: CN102964483B
Application number: CN201110259330.9A
Authority: CN
Inventors: 李传峰; 任鸿平; 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: 2015-04-08
Anticipated expiration: 2031-08-31
Also published as: CN102964483A

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 introducing a non-metallocene complex in a magnesium compound solution, treating by a chemical treatment agent and performing an in-situ reaction with a non-metallocene ligand. 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 is based on " national 11th Five-Year supporting plan problem " item understudied.This project obtains the great attention of the Ministry of Science and Technology and supports energetically, its target forms 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 that it is to the future development of variation, seriation, customizations, high performance.

Technical field

The present invention relates to a kind of non-metallocene catalyst.Specifically, 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, also known as post-metallocene catalysts, the central atom of Primary Catalysts includes nearly all transition metal, reach at some aspect of performance, even exceed metallocene catalyst, become the forth generation olefin polymerization catalysis after Ziegler, Ziegler-Natta and metallocene catalyst.The excellent property of the polyolefin products manufactured by such catalyzer, and low cost of manufacture.Non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, not containing 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 to insert and σ-key transfer, the easy alkylation of central metal, is conducive to the generation at cation activity center; The title complex formed has the geometric configuration of restriction, and stereoselectivity, electronegativity and chirality controllability, in addition, the metal-carbon key formed easily polarizes, and is more conducive to polymerization and the copolymerization of alkene.Therefore, even if the olefin polymer of higher molecular weight also can be obtained under higher polymeric reaction temperature.

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

Patent ZL 01126323.7, ZL 02151294.9ZL 02110844.7 and WO 03/010207 disclose a kind of alkene homopolymerization/copolymerization catalyzer or catalyst system, there is alkene homopolymerization/copolymerization performance widely, but the catalyzer disclosed in this patent or catalyst system in olefinic polymerization time need higher promotor consumption, suitable olefin polymerizating activity could be obtained, and it is short to there is active duration in polymerization process, polymkeric substance glues the phenomenons such as still.

Common way be by non-metallocene catalyst by certain supported technology, make loaded catalyst, thus improve the polymerization of alkene and the particle form of resulting polymers.It shows as the initial activity suitably reducing catalyzer to a certain extent, the polymerization activity life-span of extending catalyst, reduce the caking or cruelly poly-phenomenon that even avoid in polymerization process, improve the form of polymkeric substance, improve the apparent density of polymkeric substance, it can be made to meet more polymerisation process, as vapour phase polymerization or slurry polymerization etc.

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

Patent 200610026765.8 discloses a class single active center Ziegler-Natta olefin polymerizing catalyst.This catalyzer, using the salicylic alidehyde imine derivative of the salicylic alidehyde imine containing coordinating group or replacement as electron donor, obtains after pretreated carrier (as silica gel), metallic compound (as titanium tetrachloride) and electron donor carry out process by adding 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 makes magnesium compound and Nonmetallocene title complex be dissolved in solvent, add after the porous support of thermal activation treatment dry, obtain load type non-metallocene catalyst.Patent 200910180602.9 discloses a kind of preparation method of load type non-metallocene catalyst, and it makes magnesium compound and Nonmetallocene title complex be dissolved in solvent, and after adding precipitation agent, filtration washing is dry, obtains load type non-metallocene catalyst.Owing to being introducing Ziegler-Natta catalyst component in catalyst preparation process, the supported catalyst that these two kinds of methods obtain all can obtain the narrower polymkeric substance of molecular weight distribution (molecular weight distribution index of polymkeric substance is about 2 ~ 3, and the molecular weight distribution index significantly prepared lower than Ziegler-Natta catalyst is the polymkeric substance of 4 ~ 8) when carrying out olefinic polymerization catalysis.Obviously, the characteristic of polymkeric substance is determined by the character of Nonmetallocene title complex.

Load type non-metallocene catalyst preparation method disclosed in Chinese patent 200910180100.6,200910180607.1,200910180606.7,200910180605.2,200910180603.3,200910180604.8 and above-mentioned patent similar, the carrier system mixed all is used fully to mix with Nonmetallocene title complex, through super-dry or precipitation etc. non-chemically process process, obtain load type non-metallocene catalyst.Same to be determined by the character of Nonmetallocene title complex itself, the polymerization activity of such supported catalyst slightly lower than Ziegler-Natta type catalyzer, the particle form also more difficult control of polymkeric substance.

Chinese patent 200910210985.X discloses a kind of preparation method of load type non-metallocene catalyst, it makes magnesium compound and Nonmetallocene part be dissolved in solvent, the carrier modified is obtained after drying, react with chemical processing agent and modification carrier, process obtains load type non-metallocene catalyst further.Patent 200910210990.0 discloses a kind of preparation method of load type non-metallocene catalyst, it makes magnesium compound and Nonmetallocene part be dissolved in solvent, add porous support, the carrier modified is obtained after vacuumizing drying, same chemical processing agent reacts with modification carrier, and process obtains load type non-metallocene catalyst further.What these two kinds of methods adopted is in carrier by pre-dispersed for Nonmetallocene part, the non-metallocene catalyst obtained is better than supported single site catalyst in polymerization activity, in polymer performance (as molecular weight distribution), be better than Zieger-Natta catalyzer.

Load type non-metallocene catalyst preparation method disclosed in patent 200710162667.1 and above-mentioned patent similar, all use pre-dispersed for Nonmetallocene part in carrier, then be obtained by reacting load type non-metallocene catalyst with chemical processing agent, such catalyzer is better than Zieger-Natta catalyzer in polymer performance.

Patent 200710162675.6 discloses a kind of preparation method of load type non-metallocene catalyst, it is that complex carrier prepared by magnesium compound and porous support contacts with chemical processing agent and obtains a kind of Ziegler-Natta catalyst, and then prepares non-metallocene catalyst with the concurrent biochemical effect of Nonmetallocene ligand contact.Preparation method and the aforesaid method of load type non-metallocene catalyst disclosed in patent 200710162676.0 are similar, are also to prepare load type non-metallocene catalyst by Ziegler-Natta catalyst and Nonmetallocene ligand reaction.Catalyzer prepared by these two kinds of methods increases significantly in polymer performance relative to Ziegler-Natta catalyst.

Although polymer performance prepared by load type non-metallocene catalyst promotes to some extent relative 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, thus limit the industrial-scale application of load type non-metallocene catalyst.And for the composite carrier load non-metallocene catalyst that porous support and magnesium compound are formed, such as Chinese patent 200410066068.6, and based on its application patent PCT/CN2005/001737 disclosed in a kind of supported method of high reactivity non-metallocene catalyst and a kind of carry type non-metallocene calalyst for polymerization of olefine, its preparation method and application thereof, due to the existence of alcohol in system, can have a negative impact to load non-metallocene catalyst performance thereon, also limit giving full play to of non-metallocene catalyst intrinsic performance.

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 existed in prior art load type non-metallocene catalyst.

Summary of the invention

The present inventor finds through diligent research on the basis of existing technology, do not having under alcohol by using one, preparation method original position load and dip loading combined is to manufacture described load type non-metallocene catalyst, the decisive role of Nonmetallocene title complex to polymer performance can be given full play to, catalyst activity can be improved again, improve morphology, in order to solve foregoing problems, and this completes the present invention.

In the preparation method of load type non-metallocene catalyst of the present invention, do not add any proton (such as this area routine use those).In addition, in the preparation method of load type non-metallocene catalyst of the present invention, be not added to electron (in such as this area for this reason the compounds such as conventional monoesters class, di-esters, two ethers, diones and the diol-lipid used).Moreover, in the preparation method of load type non-metallocene catalyst of the present invention, also need not harsh reaction requirement and reaction conditions.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.

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

1. a preparation method for load type non-metallocene catalyst, comprises the following steps:

Make magnesium compound be dissolved in the first solvent, obtain the step of magnesium compound solution;

Make to contact with Nonmetallocene title complex through the porous support of thermal activation treatment, described magnesium compound solution, obtain the step of the first mixed serum;

First mixed serum described in convection drying, obtains the step of complex carrier;

The chemical processing agent and the described complex carrier that make to be selected from IVB race metallic compound react, and obtain the step of modifying complex carrier;

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

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 any preceding aspect, 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, methacrylate homopolymer or multipolymer, styrene homopolymers or multipolymer, the partial cross-linked form of these homopolymer or multipolymer, periodic table of elements IIA, IIIA, the refractory oxide of IVA or IVB race metal or infusibility composite oxides, 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 silicon-dioxide is selected from.

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

4. according to the preparation method described in any preceding aspect, it is characterized in that, described first solvent is selected from C _6-12aromatic hydrocarbon, halo C _6-12one or more in aromatic hydrocarbon, ester and ether, are preferably selected from C _6-12one or more in aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF), described 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 toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and tetrahydrofuran (THF) one or more, more preferably C _6-12one or more in aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).

5., according to the preparation method described in any preceding aspect, it is characterized in that, described Nonmetallocene title complex be selected from the compound with following chemical structural formula one or more:

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

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

In chemical structural formulas all above,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from periodic table of elements III-th family to XI race atoms metal, preferably IVB race 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, multiple X can be identical, also can be different, can also 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, wherein N, O, S, Se and P are coordination atom separately;

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), wherein N, O, S, Se and P are coordination atom separately;

E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are coordination atom separately;

F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;

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

Y is selected from Sauerstoffatom, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are coordination atom separately;

→ represent singly-bound or double bond;

-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 hydrogen, C independently of one another ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, is preferably formed aromatic ring, and

R ⁵be selected from lone-pair 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 ⁵for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups time, R ⁵in N, O, S, P and Se can carry out coordination as coordination atom and described center IVB race atoms metal,

Described safing function groups be selected from halogens, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, containing tin group, C ₁-C ₁₀ester group or nitro,

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

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

6., according to the preparation method described in any preceding aspect, it is characterized in that,

Described halogen is selected from F, C1, 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;

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

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

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

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

Described C ₁-C ₃₀alkyl is selected from C ₁-C ₃₀alkyl, C ₇-C ₅₀alkaryl, C ₇-C ₅₀aralkyl, C ₃-C ₃₀cyclic alkyl, C ₂-C ₃₀thiazolinyl, C ₂-C ₃₀alkynyl, C ₆-C ₃₀aryl, C ₈-C ₃₀condensed ring radical or C ₄-C ₃₀heterocyclic radical, wherein said heterocyclic radical contains the heteroatoms that 1-3 is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;

The C of described replacement ₁-C ₃₀alkyl is selected from one or more described halogen and/or described C ₁-C ₃₀the described C of alkyl alternatively base ₁-C ₃₀alkyl;

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 silicon-containing group is selected from-SiR ⁴²r ⁴³r ⁴⁴or-T-SiR ⁴⁵;

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

The described tin group that contains is selected from-SnR ⁵⁰r ⁵¹r ⁵²,-T-SnR ⁵³or-T-Sn (O) R ⁵⁴,

Described Ar represents C ₆-C ₃₀aryl, and

R ⁴⁰to R ⁵⁴be selected from hydrogen, described C independently of one another 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 any preceding aspect.

7., according to the preparation method described in any preceding aspect, it is characterized in that, described Nonmetallocene part be selected from the compound with following chemical structural formula one or more:

In chemical structural formulas all above,

Q is 0 or 1;

D is 0 or 1;

Y is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;

→ represent singly-bound or double bond;

-represent covalent linkage or ionic linkage;

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

And

Described safing function groups be selected from halogens, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, containing tin group, C ₁-C ₁₀ester group and nitro,

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

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

8., according to the preparation method described in any preceding aspect, 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;

The described tin group that contains is selected from-SnR ⁵⁰r ⁵¹r ⁵²,-T-SnR ⁵³or-T-Sn (O) R ⁵⁴;

Described R ⁴²to R ⁵⁴be selected from hydrogen, described C independently of one another 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 any preceding aspect.

9. according to the preparation method described in any preceding aspect, it is characterized in that, in the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene title complex for 1: 0.01-1, preferably 1: 0.04-0.4, more preferably 1: 0.08-0.2, in the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part for 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 first solvent is 1mol: 75 ~ 400ml, preferred 1mol: 150 ~ 300ml, more preferably 1mol: 200 ~ 250ml, in the mass ratio of the described magnesium compound of magnesium compound solid and described porous support for 1: 0.1-20, preferably 1: 0.5-10, more preferably 1: 1-5, and in the described magnesium compound of Mg element with the mol ratio of the described chemical processing agent of IVB race elemental metal for 1: 0.01-1, preferably 1: 0.01-0.50, more preferably 1: 0.10-0.30.

10. according to the preparation method described in any preceding aspect, it is characterized in that, described IVB race metallic compound be selected from IVB race metal halide, IVB race metal alkyl compound, IVB race metal alkoxide, IVB race metal alkyl halides and IVB race metal alkoxide halogenide one or more, be preferably selected from IVB race metal halide one or more, 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 any preceding aspect, is also included in and makes before described chemical processing agent and described complex carrier react, by the step helping complex carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

12. according to the preparation method described in any preceding aspect, it is characterized in that, described aikyiaiurnirsoxan beta is selected from methylaluminoxane, ethylaluminoxane, one or more in isobutyl aluminium alkoxide and normal-butyl aikyiaiurnirsoxan beta, more preferably be selected from methylaluminoxane and isobutyl aluminium alkoxide one or more, and described aluminum alkyls is selected from trimethyl aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminium, three n-pentyl aluminium, tri-n-hexyl aluminum, three isohexyl aluminium, 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 triethyl aluminum and triisobutyl aluminium one or more.

13., according to the preparation method described in any preceding aspect, is characterized in that, in the described magnesium compound of Mg element with to help the mol ratio of chemical processing agent for 1: 0-1.0 described in Al element, preferably 1: 0-0.5, more preferably 1: 0.1-0.5.

14. 1 kinds of load type non-metallocene catalysts, it is manufactured by the preparation method according to any preceding aspect.

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

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

Load type non-metallocene catalyst is manufactured according to the preparation method described in any preceding aspect, and

With described load type non-metallocene catalyst for Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt for 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 title complex and part is adjustable, can give full play to it obtains polyolefin product performance at catalysis in olefine polymerization.

Adopt method for preparing catalyst provided by the invention, because catalyzer is by introducing Nonmetallocene title complex in magnesium compound, prepare with Nonmetallocene part reaction in－situ two steps again after chemical processing agent process, in catalyzer, the controlled leeway of molar ratio of the constituent content of active metal and regular activated metal and Nonmetallocene title complex is large, thus 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 by the change of polymerizing condition, can effectively improve the performance of Olefins Product Streams, and the molecular weight distribution obtained thus is narrow and bulk density is high.

The present invention also finds, when the load type non-metallocene catalyst adopting the present invention to obtain and promotor form catalyst system, the molecular weight distribution obtained at catalysis in olefine polymerization is narrow, and during copolymerization, show significant comonomer effect, namely, 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 improving catalyst activity, the increase of porous support content then contributes to improving polymer stacks density, narrow molecular weight distribution, improves ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight.Therefore by both adjustments 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 described in detail, but it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.

In the context of the present invention, unless otherwise defined explicitly, or this implication is beyond the understanding scope of those skilled in the art, hydrocarbon more than 3 carbon atoms or hydrocarbon derivative group (such as propyl group, propoxy-, butyl, butane, butylene, butenyl, hexane etc.) not titled with all have time prefix " just " with titled with implication identical time prefix " just ".Such as, propyl group is generally understood as n-propyl, and butyl is generally understood as normal-butyl.

The present invention relates to a kind of preparation method of load type non-metallocene catalyst, comprise the following steps: make magnesium compound be dissolved in the first solvent, obtain the step of magnesium compound solution; Make to contact with Nonmetallocene title complex through the porous support of thermal activation treatment, described magnesium compound solution, obtain the step of the first mixed serum; First mixed serum described in convection drying, obtains the step of complex carrier; The chemical processing agent and the described complex carrier that make to be selected from IVB race metallic compound react, and obtain the step of modifying complex carrier; Nonmetallocene part is contacted with described modification complex carrier under the existence of the second solvent, obtains 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 " uses the common concept in this area, refers to the organic or inorganic solid water-free magnesium-containing compound of the carrier routine use as supported olefin polymerization catalyst.

According to the present invention, as described magnesium compound, magnesium halide, Alkoxymagnesium halides, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium such as can be enumerated.

Specifically, as described magnesium halide, such as magnesium chloride (MgCl can be enumerated ₂), magnesium bromide (MgBr ₂), magnesium iodide (MgI ₂) and magnesium fluoride (MgF ₂) etc., wherein preferred magnesium chloride.

As described Alkoxymagnesium halides, methoxyl group magnesium chloride (Mg (OCH such as can be enumerated ₃) Cl), oxyethyl group magnesium chloride (Mg (OC ₂h ₅) Cl), propoxy-magnesium chloride (Mg (OC ₃h ₇) Cl), n-butoxy magnesium chloride (Mg (OC ₄h ₉) Cl), isobutoxy magnesium chloride (Mg (i-OC ₄h ₉) Cl), methoxyl group magnesium bromide (Mg (OCH ₃) Br), oxyethyl group magnesium bromide (Mg (OC ₂h ₅) Br), propoxy-magnesium bromide (Mg (OC ₃h ₇) Br), n-butoxy magnesium bromide (Mg (OC ₄h ₉) Br), isobutoxy magnesium bromide (Mg (i-OC ₄h ₉) Br), methoxyl group magnesium iodide (Mg (OCH ₃) I), oxyethyl group magnesium iodide (Mg (OC ₂h ₅) I), propoxy-magnesium iodide (Mg (OC ₃h ₇) I), n-butoxy magnesium iodide (Mg (OC ₄h ₉) I) and isobutoxy magnesium iodide (Mg (i-OC ₄h ₉) I) etc., wherein preferred methoxyl group magnesium chloride, oxyethyl group magnesium chloride and isobutoxy magnesium chloride.

As described alkoxyl magnesium, magnesium methylate (Mg (OCH such as can be enumerated ₃) ₂), magnesium ethylate (Mg (OC ₂h ₅) ₂), propoxy-magnesium (Mg (OC ₃h ₇) ₂), butoxy magnesium (Mg (OC ₄h ₉) ₂), isobutoxy magnesium (Mg (i-OC ₄h ₉) ₂) and 2-ethyl hexyl oxy magnesium (Mg (OCH ₂cH (C ₂h ₅) C ₄h) ₂) etc., wherein preferred magnesium ethylate and isobutoxy magnesium.

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

As described alkyl halide magnesium, methylmagnesium-chloride (Mg (CH such as can be enumerated ₃) Cl), ethylmagnesium chloride (Mg (C ₂h ₅) Cl), propyl group magnesium chloride (Mg (C ₃h ₇) Cl), n-butylmagnesium chloride magnesium (Mg (C ₄h ₉) Cl), isobutyl-magnesium chloride (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 magnesium bromide (Mg (C ₄h ₉) Br), selenium alkynide (Mg (i-C ₄h ₉) Br), methylpyridinium iodide magnesium (Mg (CH ₃) I), ethyl phosphonium iodide magnesium (Mg (C ₂h ₅) I), propyl group magnesium iodide (Mg (C ₃h ₇) I), normal-butyl magnesium iodide (Mg (C ₄h ₉) I) and isobutyl-magnesium iodide (Mg (i-C ₄h ₉) I) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl-magnesium chloride.

As described alkyl alkoxy magnesium, methyl methoxy base magnesium (Mg (OCH such as can be enumerated 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 tert-butyl oxygen base 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)), ethylpropoxy magnesium (Mg (OC ₃h ₇) (C ₂h ₅)), ethyl n-butoxy magnesium (Mg (OC ₄h ₉) (C ₂h ₅)), ethyl isobutyl oxygen base magnesium (Mg (i-OC ₄h ₉) (C ₂h ₅)), propylmethoxy magnesium (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., wherein preferred butyl magnesium ethylate.

These magnesium compounds can be used alone one, also can be multiple used in combination, not special restriction.

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

According to the present invention, make magnesium compound be dissolved in the first solvent (not comprising alcoholic solvent), obtain magnesium compound solution.

Below the step obtaining described magnesium compound solution is specifically described.

Specifically, described magnesium compound (solid) is dissolved in suitable solvent (hereinafter sometimes referred to the solvent for dissolving described magnesium compound or the first solvent), thus obtains described magnesium compound solution.

As described first solvent, such as C can be enumerated _6-12aromatic hydrocarbon, halo C _6-12aromatic hydrocarbon, ester and ether equal solvent.

As described C _6-12aromatic hydrocarbon, such as can enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene.

As described halo C _6-12aromatic hydrocarbon, such as can enumerate chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene etc.

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

As described ether, such as ether, methyl ethyl ether, tetrahydrofuran (THF) etc. can be enumerated.

Wherein, preferred C _6-12aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF).

According to the present invention one preferred embodiment, described first solvent preferably can dissolve described magnesium compound (solid) and Nonmetallocene title complex hereinafter described simultaneously.Now, as described first solvent, such as described C can be enumerated _6-12aromatic hydrocarbon, described halo C _6-12aromatic hydrocarbon and tetrahydrofuran (THF) etc.

It is pointed out that the present invention is when preparing described load type non-metallocene catalyst, does not all use the alcohols aromatic alcohols such as fatty alcohol, phenylcarbinol etc. such as () such as ethanol in any step.

These solvents can be used alone one, also can be multiple used in combination with arbitrary ratio.

In order to prepare described magnesium compound solution, described magnesium compound (or according to circumstances, by described magnesium compound and described Nonmetallocene title complex) metering being added in described solvent and carries out dissolving.

To the preparation time (i.e. the dissolution time of described magnesium compound etc.) of described magnesium compound solution, there is no particular limitation, but be generally 0.5 ~ 24h, preferably 4 ~ 24h.In this preparation process, the dissolving of stirring and promoting described magnesium compound etc. can be utilized.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).

Below described porous support is specifically described.

According to the present invention, as described porous support, those organic or inorganic porosu solids of this area conventional use as carrier when manufacturing supported olefin polymerization catalyst such as can be enumerated.

Specifically, as described Porous-Organic solid, such as can enumerate 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, methacrylate homopolymer or multipolymer, and styrene homopolymers or multipolymer etc., and the partial cross-linked form of these homopolymer or multipolymer, the wherein styrene polymer of preferably partial cross-linked (such as degree of crosslinking is at least 2% but is less than 100%).

According to the present invention's preferred embodiment, preferably on the surface of described Porous-Organic solid with any one or the multiple active function groups that are such as 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, at least one wherein preferably in carboxyl and hydroxyl.

According to the present invention, before use thermal activation treatment is carried out to described Porous-Organic solid.This thermal activation treatment can be carried out according to common mode, such as carries out heat treated to described Porous-Organic solid at reduced pressure conditions or under inert atmosphere.Inert atmosphere mentioned here to refer in gas only containing extremely trace or containing can with the component of described Porous-Organic solid reaction.As described inert atmosphere, nitrogen or rare gas atmosphere such as can be enumerated, preferred nitrogen atmosphere.Due to the poor heat resistance of Porous-Organic solid, therefore this thermal activation process is premised on the structure not destroying described Porous-Organic solid itself and essentially consist.Usually, the temperature of this thermal activation is 50 ~ 400 DEG C, preferably 100 ~ 250 DEG C, and the thermal activation time is 1 ~ 24h, preferably 2 ~ 12h.After thermal activation treatment, described Porous-Organic solid needs malleation under an inert atmosphere to save backup.

As described inorganic porous solids, such as can enumerate the refractory oxide (such as silicon-dioxide (being also called silicon oxide or silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium white or Thorotrast etc.) of the periodic table of elements IIA, IIIA, IVA or IVB race metal, or any infusibility composite oxides of these metals (being such as oxidized 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 solids, the oxide compound generated by pyrohydrolysis by gaseous metal halide or gaseous silicon compound can also be enumerated, the silica gel such as obtained by silicon tetrachloride pyrohydrolysis, or the aluminum oxide etc. obtained by aluminum chloride pyrohydrolysis.

As described inorganic porous solids, 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 can bought arbitrarily, such as can enumerate the Grace 955 of Grace company, Grace948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245 and Aerosil812, ES70, ES70X, ES70Y, ES70W, ES757, EP10X and EP11 of Ineos company, and CS-2133 and MS-3040 of Pq Corp..

According to the present invention's preferred embodiment, preferably on the surface of described inorganic porous solids with hydroxyl isoreactivity functional group.

According to the present invention, before use thermal activation treatment is carried out to described inorganic porous solids.This thermal activation treatment can be carried out according to common mode, such as carries out heat treated to described inorganic porous solids at reduced pressure conditions or under inert atmosphere.Inert atmosphere mentioned here refers in gas and only contains extremely micro-or do not contain the component can reacted with described inorganic porous solids.As described inert atmosphere, nitrogen or rare gas atmosphere such as can be enumerated, preferred nitrogen atmosphere.Usually, the temperature of this thermal activation is 200-800 DEG C, preferably 400 ~ 700 DEG C, most preferably 400 ~ 650 DEG C, and heat-up time is such as 0.5 ~ 24h, preferably 2 ~ 12h, most preferably 4 ~ 8h.After thermal activation treatment, described inorganic porous solids needs malleation under an inert atmosphere to save backup.

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 (determination of nitrogen adsorption) of this porous support is generally 0.1 ~ 4cm ³/ g, preferably 0.2 ~ 2cm ³/ g, and its median size (laser particle analyzer mensuration) preferably 1 ~ 500 μm, more preferably 1 ~ 100 μm.

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

According to the present invention, term " Nonmetallocene title complex " is a kind of single centre olefin polymerization catalysis for metallocene catalyst, not containing the cyclopentadienyl or derivatives thereof such as luxuriant ring, fluorenes ring or indenes ring in structure, and the organometallics (therefore described Nonmetallocene title complex is also sometimes referred to as non-metallocene olefin polymerization title complex) of olefinic polymerization catalysis activity can be demonstrated when combining with promotor (than as mentioned below those).This compound comprises the polydentate ligand (preferred tridentate ligand or more tooth part) that central metal atom is combined with coordinate bond with at least one and described central metal atom, and term " Nonmetallocene part " is aforesaid polydentate ligand.

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

According to this chemical structural formula, the part forming 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 coordination atom contained by these groups heteroatomss such as () such as N, O, S, Se and P 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.

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

In one more specifically 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 to XI race atoms metal, preferably IVB race atoms metal, such as can enumerate Ti (IV), Zr (IV), Hf (IV), Cr (III), Fe (III), Ni (II), Pd (II) or Co (II);

E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group (-CN), wherein N, O, S, Se and P are coordination atom separately;

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group (-CN), such as can enumerates-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, wherein N, O, S, Se and P are coordination atom separately;

→ represent singly-bound or double bond;

-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 hydrogen, C independently of one another ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl (wherein preferred halo alkyl, such as-CH ₂cl and-CH ₂cH ₂or safing function group Cl).Above-mentioned group can be the same or different to each other, wherein adjacent group 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 ²⁶etc. key or Cheng Huan can be combined togather into, be preferably formed aromatic ring, such as unsubstituted phenyl ring or by 1-4 C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl (wherein preferred halo alkyl, such as-CH ₂cl and-CH ₂cH ₂cl) or safing function group replace phenyl 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 ⁵for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups time, R ⁵in N, O, S, P and Se can carry out coordination as coordination atom and described center IVB race 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, ring can be combined togather into, be preferably formed the heteroatomic C comprising and come 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.Described sulfur-containing group is selected from-SR ³⁵,-T-SR ³⁵,-S (O) R ³⁶or-T-SO ₂r ³⁷.The described seleno group that contains is selected from-SeR ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹or-T-Se (O) R ³⁹.Described group T is selected from C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group.Described R ³⁷be selected from hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group.

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 the heteroatoms that 1-3 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 to its relevant group combined, described C ₁-C ₃₀alkyl refers to C sometimes ₁-C ₃₀hydrocarbon two base (divalent group, or be called C ₁-C ₃₀alkylene) or C ₁-C ₃₀hydrocarbon three base (trivalent radical), 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 substituent ₁-C ₃₀alkyl.So-called inert substituent, refers to these substituting groups and aforementioned coordinative group (is referred to aforementioned group A, D, E, F, Y and Z, or also optionally comprises radicals R ⁵) there is no substantial interference with the complexation process of described central metal atom M; In other words, the chemical structure by polydentate ligand of the present invention limit, and these substituting groups do not have ability or have no chance (being such as subject to the impact of steric hindrance etc.) coordination reaction occurs with described central metal atom M and forms coordinate bond.Generally speaking, described inert substituent is such as 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 can enumerate be selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, containing tin group, C ₁-C ₁₀ester group or nitro (-NO ₂) at least one etc.

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

(1) complexation process of described group A, D, E, F, Y or Z and described central metal atom M is not disturbed, 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 ^-; Described silicon-containing group is selected from-SiR ⁴²r ⁴³r ⁴⁴or-T-SiR ⁴⁵; Described germanic group is selected from-GeR ⁴⁶r ⁴⁷r ⁴⁸or-T-GeR ⁴⁹; The described tin group that contains is selected from-SnR ⁵⁰r ⁵¹r ⁵²,-T-SnR ⁵³or-T-Sn (O) R ⁵⁴, wherein Ar represents C ₆-C ₃₀aryl.R ⁴⁰to R ⁵⁴be selected from hydrogen, aforesaid C independently of one another ₁-C ₃₀the C of alkyl, aforesaid replacement ₁-C ₃₀alkyl or aforesaid safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan.Wherein, the definition of group T is the same.

As described Nonmetallocene title complex, such as following compound can be enumerated:

Described Nonmetallocene title complex is preferably selected from following compound:

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

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

These Nonmetallocene title complexs can be used alone one, or use multiple with arbitrary ratio combination.

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 manufacture according to any method well known by persons skilled in the art.About the particular content of its manufacture method, such as can see WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 etc., this specification sheets introduces the full text of these documents as a reference at this point.

According to the present invention, make the described porous support through thermal activation treatment, described magnesium compound solution contacts with described Nonmetallocene title complex, obtain the first mixed serum.

When manufacturing described first mixed serum, to the way of contact and engagement sequence etc. of the described porous support through thermal activation treatment, described magnesium compound solution and described Nonmetallocene title complex, there is no particular limitation, such as can enumerate and the described porous support through thermal activation treatment is first mixed with described magnesium compound solution, and then add the scheme of described Nonmetallocene title complex wherein; Make the scheme that the described porous support through thermal activation treatment, described magnesium compound solution and described Nonmetallocene title complex mix simultaneously; Or preferably, described Nonmetallocene title complex and described magnesium compound is made to be dissolved in foregoing first solvent, manufacture the mixing solutions (hereinafter sometimes also referred to as magnesium compound solution) of magnesium compound and Nonmetallocene title complex thus, and then make described scheme mixed with described mixing solutions through the porous support of thermal activation treatment etc.

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

Now, the first mixed serum obtained is a kind of system of pulpous state.Although unrequired, in order to ensure the homogeneity of system, this first mixed serum preferably carries out the airtight of certain hour (2 ~ 48h, preferably 4 ~ 24h, most preferably 6 ~ 18h) after the production and leaves standstill.

By to described first mixed serum convection drying, a kind of solid product of good fluidity can be obtained, i.e. complex carrier of the present invention.

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

Below described chemical processing agent is specifically described.

According to the present invention, using IVB race metallic compound as described chemical processing agent.

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

As described IVB race metal halide, described IVB race metal alkyl compound, described IVB race metal alkoxide, described IVB race metal alkyl halides and described IVB race metal alkoxide halogenide, the compound of following formula such as can be enumerated:

M(OR ¹) _mX _nR ² _4-m-n

Wherein:

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

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

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

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

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

Specifically, as described IVB race metal halide, such as titanium tetrafluoride (TiF can be enumerated 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 (Hfl ₄).

As described IVB race metal alkyl compound, tetramethyl-titanium (Ti (CH such as can be enumerated 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 methyl titanium (Ti (CH ₃) (CH ₃cH ₂) ₃), diethyl-dimethyl titanium (Ti (CH ₃) ₂(CH ₃cH ₂) ₂), trimethylethyl 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 methyl zirconium (Zr (CH ₃) (CH ₃cH ₂) ₃), diethyl-dimethyl zirconium (Zr (CH ₃) ₂(CH ₃cH ₂) ₂), trimethylethyl 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 methyl hafnium (Hf (CH ₃) (CH ₃cH ₂) ₃), diethyl-dimethyl hafnium (Hf (CH ₃) ₂(CH ₃cH ₂) ₂), trimethylethyl 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 race metal alkoxide, tetramethoxy titanium (Ti (OCH such as can be enumerated 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 race metal alkyl halides, trimethyl ammonia chloride titanium (TiCl (CH such as can be enumerated ₃) ₃), triethyl titanium chloride (TiCl (CH ₃cH ₂) ₃), triisobutyl titanium chloride (TiCl (i-C ₄h ₉) ₃), three n-butylmagnesium chloride 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 n-butylmagnesium chloride 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 titanium bromide (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 titanium bromide (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);

Trimethyl ammonia chloride zirconium (ZrCl (CH ₃) ₃), triethyl zirconium chloride (ZrCl (CH ₃cH ₂) ₃), triisobutyl zirconium chloride (ZrCl (i-C ₄h ₉) ₃), three n-butylmagnesium chloride 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 n-butylmagnesium chloride 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 zirconium bromide (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 zirconium bromide (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);

Trimethyl ammonia chloride hafnium (HfCl (CH ₃) ₃), triethyl hafnium chloride (HfCl (CH ₃cH ₂) ₃), triisobutyl hafnium chloride (HfCl (i-C ₄h ₉) ₃), three n-butylmagnesium chloride 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 n-butylmagnesium chloride 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 (i-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 race metal alkoxide halogenide, trimethoxy titanium chloride (TiCl (OCH such as can be enumerated 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), methoxytitanium trichloride (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), nbutoxytitanium trichloride (Ti (OC ₄h ₉) Cl ₃);

Trimethoxy titanium bromide (TiBr (OCH ₃) ₃), triethoxy titanium bromide (TiBr (OCH ₃cH ₂) ₃), three isobutoxy titanium bromide (TiBr (i-OC ₄h ₉) ₃), three n-butoxy titanium bromide (TiBr (OC ₄h ₉) ₃), dimethoxy dibrominated titanium (TiBr ₂(OCH ₃) ₂), diethoxy dibrominated titanium (TiBr ₂(OCH ₃cH ₂) ₂), two isobutoxy dibrominated titanium (TiBr ₂(i-OC ₄h ₉) ₂), three n-butoxy titanium bromide (TiBr (OC ₄h ₉) ₃), methoxyl group titanium tribromide (Ti (OCH ₃) Br ₃), 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 race metallic compound, preferred described IVB race metal halide, more preferably TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄and HfBr ₄, most preferably TiCl ₄and ZrCl ₄.

These IVB race metallic compounds can be used alone one, or use multiple with arbitrary ratio combination.

According to the present invention, the chemical processing agent and the described complex carrier that make to be selected from described IVB race metallic compound react (chemical treatment is reacted), obtain and modify complex carrier.

When described chemical processing agent is liquid at normal temperatures, can by using described chemical processing agent to the mode of the described chemical processing agent having directly dropping predetermined amount in the reaction object of this chemical processing agent process to be utilized (than complex carrier as the aforementioned).

When described chemical processing agent is solid-state at normal temperatures, in order to measure with easy to operate for the purpose of, preferably use described chemical processing agent as a solution.Certainly, when described chemical processing agent is liquid at normal temperatures, sometimes also can uses described chemical processing agent as a solution as required, be not particularly limited.

When preparing the solution of described chemical processing agent, to now used solvent, there is no particular limitation, as long as it can dissolve this chemical processing agent.

Specifically, C can be enumerated _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 can enumerate pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, pentamethylene, hexanaphthene, suberane, cyclooctane, toluene, ethylbenzene, dimethylbenzene, chloro-pentane, chloro-hexane, chloro heptane, chloro octane, chloro nonane, chloro decane, chloro undecane, chlorinated dodecane, chlorocyclohexane, chlorotoluene, chloro ethylbenzene and xylene monochloride etc., wherein preferred pentane, hexane, decane, hexanaphthene and toluene, most preferably hexane and toluene.

These solvents can be used alone one, or use multiple with arbitrary ratio combination.

In addition, to the concentration of described chemical processing agent in its solution, there is no particular limitation, can suitably select as required, as long as it can realize with the described chemical processing agent of predetermined amount to implement described chemical treatment.As previously mentioned, if chemical processing agent is liquid, chemical processing agent directly can be used to carry out described process, 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 can enumerate, when chemical processing agent is solid-state (such as zirconium tetrachloride), first the solution of described chemical processing agent is prepared, then in pending reaction object (than complex carrier as the aforementioned), the described solution of (preferably dripping) the described chemical processing agent containing predetermined amount is added, to carry out chemical treatment reaction.When chemical processing agent is liquid (such as titanium tetrachloride), directly the described chemical processing agent of predetermined amount can be added in (preferably dripping) pending reaction object (than complex carrier as the aforementioned), to carry out chemical treatment reaction, or after this chemical processing agent is prepared into solution, the described solution of (preferably dripping) the described chemical processing agent containing predetermined amount is added, to carry out chemical treatment reaction in pending reaction object (than complex carrier as the aforementioned).

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

After chemical treatment reaction terminates, by filtering, washing and drying, can obtain through chemically treated product.

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

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

That is, according to the present invention, after the reaction of the described chemical processing agent of use terminates, by aforesaid filtration, washing and drying, obtained process product is separated completely, and then use this process product to carry out next step reaction or process.

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

According to the present invention, group A, D and E (coordination group) in this compound form coordinate bond by the IVB race atoms metal generation coordination reaction contained by the IVB race metallic compound that uses as chemical processing agent in coordination atom contained by it heteroatomss such as () such as N, O, S, Se and P and the present invention, form the title complex (i.e. Nonmetallocene title complex of the present invention) of atoms metal centered by this IVB race atoms metal thus.

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

In one more specifically 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;

→ represent singly-bound or double bond;

-represent covalent linkage or ionic linkage.

R ¹to R ⁴, R ⁶to R ³⁶, R ³⁸and R ³⁹be selected from hydrogen, C independently of one another ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl (wherein preferred halo alkyl, such as-CH ₂cl and-CH ₂cH ₂or safing function group Cl).Above-mentioned group can be the same or different to each other, wherein adjacent group 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 ²⁶etc. key or Cheng Huan can be combined togather into, be preferably formed aromatic ring, such as unsubstituted phenyl ring or by 1-4 C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl (wherein preferred halo alkyl, such as-CH ₂cl and-CH ₂cH ₂cl) or safing function group replace phenyl ring.

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 ¹⁹,-P (O) R ³⁰r ³¹or-P (O) R ³²(OR ³³).Described oxy radical is selected from hydroxyl ,-OR ³⁴with-T-OR ³⁴.Described sulfur-containing group is selected from-SR ³⁵,-T-SR ³⁵,-S (O) R ³⁶or-T-SO ₂r ³⁷.The described seleno group that contains is selected from-SeR ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹or-T-Se (O) R ³⁹.Described group T is selected from C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group.Described R ³⁷be selected from hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group.

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 substituent ₁-C ₃₀alkyl.So-called inert substituent, refers to these substituting groups and aforementioned coordinative group (is referred to aforementioned group A, D, E, F, Y and Z, or also optionally comprises R ⁵) there is no substantial interference with the complexation process of central metal atom (aforementioned IVB race atoms metal); In other words, the chemical structure by part of the present invention limit, and these substituting groups do not have ability or have no chance (being such as subject to the impact of steric hindrance etc.) and the atoms metal generation coordination reaction of described IVB race and form coordinate bond.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 can enumerate be selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, containing tin group, C ₁-C ₁₀ester group and nitro (-NO ₂) at least one etc.

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

(1) complexation process of described group A, D, E, F, Y or Z and described IVB race atoms metal is not disturbed, and

(2) with the coordination ability of described IVB race 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 race atoms metal.

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

As described Nonmetallocene part, such as following compound can be enumerated:

Described Nonmetallocene part is preferably selected from following compound:

Described Nonmetallocene part is preferably selected from following compound further:

Described Nonmetallocene part is more preferably selected from following compound:

These Nonmetallocene parts can be used alone one, or use multiple with arbitrary ratio combination.

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 manufacture according to any method well known by persons skilled in the art.About the particular content of its manufacture method, such as can see WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 etc., this specification sheets introduces the full text of these documents as a reference at this point.

Then, described modification complex carrier is contacted (contact reacts) with described Nonmetallocene part under the existence of the second solvent, described second mixed serum can be obtained.

According to the present invention, described Nonmetallocene part and described modification complex carrier are reacted, cause afore mentioned chemical treatment agent generation coordination reaction contained on described Nonmetallocene part and this modification complex carrier, thus on this modification complex carrier the Nonmetallocene title complex (the supported reaction of original position) of in-situ preparation atoms metal centered by this IVB race atoms metal, this is of the present invention one large feature.

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

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

Now, the second mixed serum obtained is a kind of system of pulpous state.Although unrequired, in order to ensure the homogeneity of system, this second mixed serum preferably carries out the airtight of certain hour (2 ~ 48h, preferably 4 ~ 24h, most preferably 6 ~ 18h) after the production and leaves standstill.

According to the present invention, when manufacturing described second mixed serum, to described second solvent (hereinafter sometimes referred to dissolving Nonmetallocene part solvent), there is no particular limitation, as long as it can dissolve described Nonmetallocene part.As described second solvent, such as C can be enumerated _6-12aromatic hydrocarbon, halo C _6-12aromatic hydrocarbon, halo C _1-10alkane, one or more in ester and ether.Specifically such as can enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and tetrahydrofuran (THF) etc.Wherein, preferred C _6-12aromatic hydrocarbon, tetrahydrofuran (THF) and methylene dichloride.

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

According to the present invention, to the consumption of described second solvent without any restriction, as long as be enough to realize the amount that described modification complex carrier fully contacts with described Nonmetallocene part.Such as, easily, described Nonmetallocene part is generally 0.02 ~ 0.30 grams per milliliter relative to the ratio of described second solvent, preferably 0.05 ~ 0.15 grams per milliliter, but is sometimes not limited to this.

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

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

According to the present invention's special embodiment, the preparation method of load type non-metallocene catalyst of the present invention is also included in and makes before described chemical processing agent and described complex carrier react, by the step (pre-treatment step) helping complex carrier described in chemical processing agent pre-treatment being 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, help chemical processing agent as described, such as can enumerate aikyiaiurnirsoxan beta and aluminum alkyls.

As described aikyiaiurnirsoxan beta, such as can enumerate the linear alumoxanes shown in following general formula (I): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the Cyclic aluminoxane 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 C independently of one another ₁-C ₈alkyl, preferable methyl, ethyl and isobutyl-, most preferable; N is the arbitrary integer within the scope of 1-50, the arbitrary integer preferably in 10 ~ 30 scopes.

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

These aikyiaiurnirsoxan beta can be used alone one, or use multiple with arbitrary ratio combination.

As described aluminum alkyls, such as the compound shown in following general formula can be enumerated:

Al(R) ₃

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

Specifically, as described aluminum alkyls, trimethyl aluminium (Al (CH such as can be enumerated ₃) ₃), triethyl aluminum (Al (CH ₃cH ₂) ₃), tri-n-n-propyl aluminum (Al (C ₃h ₇) ₃), triisopropylaluminiuand (Al (i-C ₃h ₇) ₃), triisobutyl aluminium (Al (i-C ₄h ₉) ₃), three n-butylaluminum (Al (C ₄h ₉) ₃), triisopentyl aluminium (Al (i-C ₅h ₁₁) ₃), three n-pentyl aluminium (Al (C ₅h ₁₁) ₃), tri-n-hexyl aluminum (Al (C ₆h ₁₃) ₃), three isohexyl aluminium (Al (i-C ₆h ₁₃) ₃), diethylmethyl aluminium (Al (CH ₃) (CH ₃cH ₂) ₂) and dimethyl ethyl aluminium (Al (CH ₃cH ₂) (CH ₃) ₂) etc., wherein preferred trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.

These aluminum alkylss can be used alone one, or use multiple with arbitrary ratio combination.

According to the present invention, help chemical processing agent as described, 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 component each in this mixture, there is no particular limitation, can select arbitrarily as required.

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

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

Through described pre-treatment step, obtain thus through pretreated complex carrier.Then, then carry out reacting with aforementioned same chemical treatment with described chemical processing agent according to aforementioned identical mode, just described complex carrier is replaced with described through pretreated complex carrier.

Namely, by reacting with aforementioned same chemical treatment, make to be selected from the chemical processing agent of described IVB race metallic compound and describedly react to manufacture modification complex carrier through pretreated complex carrier, and manufacturing load type non-metallocene catalyst of the present invention according to mode same before further.

As the method for carrying out described pre-treatment step, such as can enumerate, first the solution of chemical processing agent is helped described in preparing, then help in the pretreated described complex carrier of chemical processing agent described in using to plan to be metered into described in (preferably dripping) and help chemical treatment agent solution (wherein helping chemical processing agent containing described in predetermined amount), or add described complex carrier, forming reactions mixed solution thus to the described chemical treatment agent solution amount of falling into a trap that helps.Now, temperature of reaction is generally-40 ~ 60 DEG C, and preferably-30 ~ 30 DEG C, the reaction times is generally 1 ~ 8h, preferably 2 ~ 6h, most preferably 3 ~ 4h (if desired by stirring).Then, by filtering, washing and optionally drying, from this reaction mixture, pretreatment product is isolated.

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

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

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

According to the present invention, as the consumption of described Nonmetallocene part, make to reach 1: 0.0001-1 in the described magnesium compound (solid) of Mg element and the mol ratio of described Nonmetallocene part, 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 the consumption of described solvent for dissolving described magnesium compound or described first solvent, described magnesium compound (solid) is made to reach 1mol: 75 ~ 400ml with the ratio of described first solvent, preferred 1mol: 150 ~ 300ml, more preferably 1mol: 200 ~ 250ml.

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

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

According to the present invention, as the described consumption helping 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: 0-1.0 described in Al element, preferably 1: 0-0.5, more preferably 1: 0.1-0.5.

Known to those skilled in the art, aforementioned all method stepss are all preferred to carry out under the condition of anhydrous and oxygen-free substantially.Substantially the content that anhydrous and oxygen-free mentioned here refers to water and oxygen in system 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 after the production usually.

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) manufactured by the preparation method of aforesaid load type non-metallocene catalyst.

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

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

Primary Catalysts and promotor can be first add Primary Catalysts to the feed postition in polymerization reaction system, and then add promotor, or first add promotor, and then add Primary Catalysts, or both first contact mixing after add together, or to add respectively simultaneously.Primary Catalysts and promotor are added respectively and fashionablely both can to add successively in same Feed lines, also can add successively in multichannel Feed lines, and both add respectively simultaneously and fashionablely should select multichannel Feed lines.For continous way polyreaction, preferred multichannel Feed lines adds simultaneously continuously, and for intermittence type polymerization reaction, preferably adds together in same Feed lines after both first mixing, or in same Feed lines, first add promotor, and then add Primary Catalysts.

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

Specifically, as described C ₂~ C ₁₂monoolefine, such as can enumerate 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 1-cyclopentenes and norbornylene etc. can be enumerated; As described diolefin, Isosorbide-5-Nitrae-divinyl, 2,5-pentadienes, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc. such as can be enumerated; And as other ethylenically unsaturated compounds described, vinyl acetate and (methyl) acrylate etc. such as can be enumerated.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 the polymerization of only a kind 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 can enumerate the linear alumoxanes shown in following general formula (I-1): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the Cyclic aluminoxane 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 C independently of one another ₁-C ₈alkyl, preferable methyl, ethyl and isobutyl-, most preferable.N is the arbitrary integer within the scope of 1-50, the arbitrary integer preferably in 10 ~ 30 scopes.

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

Al(R) ₃

Specifically, as described aluminum alkyls, trimethyl aluminium (Al (CH such as can be enumerated 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 most preferably triethyl aluminum.

As described haloalkyl aluminium, such as the compound shown in following general formula can be enumerated:

Al(R) _nX _3-n

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

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

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

These haloalkyl aluminium can be used alone one, or use multiple with arbitrary ratio combination.

As described boron fluothane, described boron alkyl and described boron alkyl ammonium salt, directly can use those of this area routine use, not special restriction.

In addition, according to the present invention, described promotor can be used alone one, also can use multiple aforesaid promotor with arbitrary ratio combination as required, not special restriction.

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

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

As described solvent for polymerization, such as C can be enumerated _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, pentane, hexane, heptane and cyclohexane give is preferably used to be described solvent for polymerization, most preferably hexane.

These solvent for polymerization can be used alone one, or use multiple with arbitrary ratio combination.

According to the present invention, the polymerization pressure of described alkene homopolymerization/copolymerization method is generally 0.1 ~ 10MPa, preferably 0.1 ~ 4MPa, more preferably 0.4 ~ 3MPa, but is sometimes not limited to this.According to the present invention, polymeric reaction temperature is generally-40 DEG C ~ 200 DEG C, preferably 10 DEG C ~ 100 DEG C, more preferably 40 DEG C ~ 95 DEG C, but is sometimes not limited to this.

In addition, according to the present invention, described alkene homopolymerization/copolymerization method can be carried out having under hydrogen existent condition, also can not have to carry out under hydrogen existent condition.In case of presence, 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 method, in the described promotor of aluminium or boron be generally 1 ~ 1000: 1 in the mol ratio of the described load type non-metallocene catalyst of described central metal atom, preferably 10 ~ 500: 1, more preferably 15 ~ 300: 1, but be sometimes not limited to this.

Embodiment

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

(unit is g/cm to polymer stacks density ³) mensuration carry out with reference to CNS GB 1636-79.

In load type non-metallocene catalyst, the content of IVB race 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 terminates, polymerisate in reactor is filtered and drying, then weigh the quality of this polymerisate, represent the polymerization activity (unit is kg polymkeric substance/g catalyzer or kg polymkeric substance/gCat) of this catalyzer with this polymerisate quality divided by the ratio of the quality of load type non-metallocene catalyst used.

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

The viscosity-average molecular weight of polymkeric substance calculates 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 solvent is perhydronaphthalene, measuring temperature is 135 DEG C) measure the limiting viscosity of described polymkeric substance, then according to the viscosity-average molecular weight Mv of polymkeric substance described in following formulae discovery.

Mv＝5.37×10 ⁴×[η] ^1.37

Wherein, η is limiting viscosity.

Embodiment 1

Magnesium compound adopts Magnesium Chloride Anhydrous, and Nonmetallocene title complex employing structure is compound, the first solvent adopts dimethylbenzene, and porous support adopts silicon-dioxide, i.e. silica gel, and model is the ES757 of Ineos company, first by silica gel 600 DEG C, continue roasting 4h and thermal activation under nitrogen atmosphere.IVB race chemical processing agent adopts titanium tetrachloride (TiCl ₄), the second solvent adopts methylene dichloride, and Nonmetallocene part employing structure is compound.

Take 5 grams of magnesium compounds, after joining the first solvent, add Nonmetallocene title complex again, dissolve completely at normal temperatures and obtain magnesium compound solution, then add the porous support of thermal activation, stir after 2 hours, obtain the first mixed serum, then be uniformly heated to 90 DEG C, directly vacuumize drying, obtain complex carrier.

Join in hexane solvent by obtained complex carrier, normal temperature is added dropwise to chemical processing agent in lower 30 minutes, is then uniformly heated to 60 DEG C of isothermal reactions after 2 hours, filter, hexane solvent washs 3 times, each 60ml, finally at 60 DEG C, vacuumize drying, obtain modifying complex carrier.

At room temperature, Nonmetallocene part is joined in the second solvent, then add modification complex carrier, stir 4 hours, more airtight leaving standstill directly vacuumized drying after 12 hours, obtained 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, is 1mol: 210ml with the proportioning of the first solvent, is 1: 0.20 with chemical processing agent mol ratio, and 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:

Make before chemical processing agent and complex carrier react, help complex carrier described in chemical processing agent pre-treatment with triethyl aluminum and obtain pretreated complex carrier.

Namely, complex carrier is joined in hexane solvent, slowly drip again and help chemical processing agent triethyl aluminum (concentration is 0.88mol/L, hexane solution), stir at 60 DEG C after 2 hours and filter, hexanes wash 3 times, each 60ml, finally at 60 DEG C, vacuumize drying, obtain pretreated complex carrier.Wherein magnesium compound with help the mol ratio of chemical processing agent to be 1: 0.2.

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

Embodiment 3

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

Make before chemical processing agent and complex carrier react, help complex carrier described in chemical processing agent pre-treatment by methylaluminoxane and obtain pretreated complex carrier.

Namely, complex carrier is joined in toluene solvant, slowly drip again and help chemical processing agent methylaluminoxane (concentration is 10wt%, toluene solution), stir at 60 DEG C after 2 hours and filter, toluene wash 3 times, each 60ml, finally at 100 DEG C, vacuumize drying, obtain pretreated complex carrier.Wherein magnesium compound with help the mol ratio of chemical processing agent to be 1: 0.4.

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), Nonmetallocene title complex adopts toluene changed into by first solvent, and porous support changes into 955 of Grace company, 400 DEG C, continue roasting 8h and thermal activation under nitrogen atmosphere.Chemical processing agent changes zirconium tetrachloride (ZrCl into ₄).

Nonmetallocene part adopts second solvent changes toluene into, and the first mixed serum is changed into and directly vacuumize drying at 100 DEG C.

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; Be 1mol: 150ml with the proportioning of the first solvent; Be 1: 0.30 with chemical processing agent mol ratio; 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 changes into anhydrous magnesium bromide (MgBr ₂), Nonmetallocene title complex adopts tetrahydrofuran (THF) changed into by first solvent and the second solvent.Porous support adopts aluminium sesquioxide.By aluminium sesquioxide 700 DEG C, continue roasting 6h under nitrogen atmosphere.Chemical processing agent changes titanium tetrabromide (TiBr into ₄),

Nonmetallocene part adopts first mixed serum is changed into and directly vacuumize drying at 110 DEG C.

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; Be 1mol: 280ml with the proportioning of the first solvent; Be 1: 0.10 with chemical processing agent mol ratio; 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 changes into magnesium ethylate (Mg (OC ₂h ₅) ₂), Nonmetallocene title complex adopts porous support adopts silica-magnesia mixed oxide (mass ratio 1: 1).By silica-magnesia mixed oxide 600 DEG C, continue roasting 4h under argon gas atmosphere.

Nonmetallocene part adopts xylene monochloride changed into by first solvent.Chemical processing agent changes into tetraethyl-titanium (Ti (CH ₃cH ₂) ₄), the first mixed serum is changed into and directly vacuumize drying at 120 DEG C.

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; Be 1mol: 200ml with the proportioning of the first solvent; Be 1: 0.15 with chemical processing agent mol ratio; 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 changes into magnesium ethide (Mg (C ₂h ₅) ₂), Nonmetallocene title complex adopts porous support adopts polynite.By polynite 400 DEG C, continue roasting 8h under nitrogen atmosphere.Chemical processing agent changes into tetra-n-butyl titanium (Ti (C ₄h ₉) ₄), Nonmetallocene part adopts diethylbenzene changed into by first solvent.First mixed serum is changed into and directly vacuumize drying at 130 DEG C.

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; Be 1: 0.50 with chemical processing agent mol ratio; 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 changes into ethylmagnesium chloride (Mg (C ₂h ₅) Cl), porous support adopts the polystyrene of partial cross-linked (degree of crosslinking is 30%).By this polystyrene 85 DEG C, continue under nitrogen atmosphere to dry 12h.Nonmetallocene title complex adopts nonmetallocene part adopts chemical processing agent changes into three isobutoxy titanium chloride (TiCl (i-OC ₄h ₉) ₃), toluene changed into by the first solvent.

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; Be 1mol: 210ml with the proportioning of the first solvent; Be 1: 0.20 with chemical processing agent mol ratio; 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 changes into normal-butyl magnesium ethylate (Mg (OC ₂h ₅) (C ₄h ₉)), Nonmetallocene title complex adopts porous support adopts diatomite.By diatomite 500 DEG C, continue roasting 8h under nitrogen atmosphere.Chemical processing agent changes into purity titanium tetraethoxide (Ti (OCH ₃cH ₂) ₄), Nonmetallocene part adopts chlorotoluene changed into by first solvent.

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 changes into oxyethyl group magnesium chloride (Mg (OC ₂h ₅) Cl), Nonmetallocene title complex adopts porous support adopts titanium dioxide.By titanium dioxide 300 DEG C, continue roasting 6h under nitrogen atmosphere.

Nonmetallocene part adopts chemical processing agent changes into diethyl-dimethyl titanium (Ti (CH ₃) ₂(CH ₃cH ₂) ₂), ethylbenzene changed into by the first solvent, and tetrahydrofuran (THF) changed into by the second solvent.

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

Reference example A

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

Nonmetallocene title complex is not added in load type non-metallocene catalyst preparation process;

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

Reference example B

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

The step of modifying complex carrier and Nonmetallocene ligand contact is omitted in load type non-metallocene catalyst preparation process;

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 change 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 change 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 change into 1: 0.2;

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

Application Example

Load type non-metallocene catalyst CAT-1 ~ 10 obtained in the embodiment of the present invention, CAT-A ~ E are carried out respectively under the following conditions in accordance with the following methods 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, polymerization temperature 85 DEG C, 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 terminates, by gas reactor emptying, release still interpolymer, after drying, weigh quality.Particular case and the polymerization evaluation result of this polyreaction 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, polymerization temperature 85 DEG C, 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, disposablely add hexene-1 comonomer 50g, add hydrogen again to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction terminates, by gas reactor emptying, release still interpolymer, after drying, weigh quality.Particular case and the polymerization evaluation result of this polyreaction are as shown in table 1.

Prepare ultrahigh molecular weight polyethylene(UHMWPE) to be polymerized to: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.5MPa, polymerization temperature 70 DEG C, 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 terminates, by gas reactor emptying, release still interpolymer, after drying, weigh quality.Particular case and the polymerization evaluation result of this polyreaction are as shown in table 2.

From table 1, it is narrower that the load type non-metallocene catalyst prepared by method provided by the invention is polymerized the molecular weight distribution obtained, those skilled in the art know, general employing Ziegler-Natta catalyst is polymerized the molecular weight of polyethylene distribution obtained and is greater than 5.

Known by the test-results data of sequence number in table 11 and 3,5 and 7,8 and 10, increase the consumption of promotor, namely improve promotor and catalyst activity metal molar than time, impact that is active on polymerization catalyst and polymer stacks density is not remarkable.It can be said that bright, the load type non-metallocene catalyst adopting method provided by the invention to prepare only needs fewer promotor consumption just can obtain high olefin polymerizating activity; And the polymkeric substance such as obtained polyethylene has excellent polymer morphology and high polymer bulk density thus.

In contrast table 1, the test-results data of sequence number 1 and 2,5 and 6,8 and 9 are known, after copolymerization, catalyst activity has increase by a relatively large margin, thus illustrates that the load type non-metallocene catalyst adopting 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 sequence number 1 and 9 test-results data are known in table 2, the add-on of Nonmetallocene title complex is increased in catalyzer, although polymer stacks density decreases, but its activity increases thereupon, molecular weight distribution sharp, sequence number 1 and comparative example sequence number 18 and 19 in associative list 1, do not add Nonmetallocene title complex or do not add Nonmetallocene part in sequence number 1 and contrast sequence number 7 and 8 catalyst preparation process in table 2, 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, the catalyzer of different activities and polymer performance can be obtained by the add-on changing Nonmetallocene title complex and part.

By sequence number 1 in contrast table 1 and comparative example sequence number 21 and 22, and the test-results data of sequence number 1 and comparative example 10 and 11 are known in table 2, reduce and increase the proportioning of magnesium compound and porous support in catalyzer, catalyst activity reduces or increases, polymer stacks density increases or reduces, polymericular weight narrows or broadens, thus illustrate that the raising of magnesium compound content is conducive to improving catalyst activity, the increase of porous support content then contributes to improving polymer stacks density, narrow molecular weight distribution, improves ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight.Therefore one skilled in the art will appreciate that by both adjustments proportioning, just can regulate catalysis in olefine polymerization activity, polymer stacks density and molecular weight and distribution thereof.

Although be described in detail the specific embodiment of the present invention above in conjunction with the embodiments, it is pointed out that protection scope of the present invention not by the restriction of these embodiments, but determined by claims of annex.Those skilled in the art can carry out suitable change to these embodiments in the scope not departing from technological thought of the present invention and purport, and the embodiment after these changes is obviously also included within protection scope of the present invention.

Claims

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

Wherein, this preparation method is optionally also included in and makes before described chemical processing agent and described complex carrier react, by the step helping complex carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

2. according to preparation method according to 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, methacrylate homopolymer or multipolymer, styrene homopolymers or multipolymer, the partial cross-linked form of these homopolymer or multipolymer, periodic table of elements IIA, IIIA, the refractory oxide of IVA or IVB race metal or infusibility composite oxides, clay, molecular sieve, mica, polynite, one or more in wilkinite and diatomite.

3. according to preparation method according to claim 2, it is characterized in that, described porous support be selected from partial cross-linked styrene polymer, silicon-dioxide, aluminum oxide, magnesium oxide, oxidation sial, oxidation magnalium, titanium dioxide, molecular sieve and polynite one or more.

4., according to preparation method according to claim 1, it is characterized in that, described magnesium compound be selected from magnesium halide, Alkoxymagnesium halides, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium one or more.

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

6. according to preparation method according to claim 1, it is characterized in that, described first solvent is selected from C _6-12aromatic hydrocarbon, halo C _6-12one or more in aromatic hydrocarbon, ester and ether, described 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 according to claim 6, it is characterized in that, described first solvent is selected from C _6-12one or more in aromatic hydrocarbon and tetrahydrofuran (THF), described second solvent is selected from C _6-12one or more in aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).

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

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 to XI race atoms metal;

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

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 P are coordination atom separately;

→ represent singly-bound or double bond;

-represent covalent linkage or ionic linkage;

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

R ¹to R ³be selected from hydrogen, C independently of one another ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group, R ²²to R ³³and R ³⁹be selected from hydrogen, C independently of one another 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,

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 the heteroatoms that 1-3 is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;

The C of described replacement ₁-C ₃₀alkyl is selected from one or more aforementioned halogen or aforementioned C ₁-C ₃₀the aforementioned C of alkyl alternatively base 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 hydrogen, aforementioned C independently of one another 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.

9., according to preparation method according to claim 8, it is characterized in that, described Nonmetallocene title complex be selected from the compound (A) and compound (B) with following chemical structural formula one or more:

In chemical structural formulas all above,

F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately.

10. according to preparation method according to claim 9, it is characterized in that, 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 one or more in compound (B-4):

In chemical structural formulas all above,

R ⁴, R ⁶to R ²¹be selected from hydrogen, C independently of one another ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, 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 ⁵for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups time, R ⁵in N, O, S, P and Se can carry out coordination as coordination atom and center IVB race atoms metal.

11., according to preparation method according to claim 1, is characterized in that, described Nonmetallocene title complex be selected from the compound with following chemical structural formula one or more:

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

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

In above chemical structural formula,

Q is 0 or 1;

D is 0 or 1;

→ represent singly-bound or double bond;

-represent covalent linkage or ionic linkage;

The C of described replacement ₁-C ₃₀alkyl is selected from one or more halogen or C ₁-C ₃₀the aforementioned C of alkyl alternatively base 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;

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

Described R ³⁴to R ³⁶, R ³⁸and R ⁴²to R ⁵⁴be selected from hydrogen, aforementioned C independently of one another 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.

14., according to preparation method according to claim 13, is characterized in that, described Nonmetallocene part be selected from the compound (A) and compound (B) with following chemical structural formula one or more:

In chemical structural formulas all above,

F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately.

15. according to preparation method according to claim 14, it is characterized in that, described Nonmetallocene part is selected from the compound (A-1) with following chemical structural formula to compound (A-4) and compound (B-1) to one or more in compound (B-4):

In chemical structural formulas all above,

R ⁴, R ⁶to R ²¹be selected from hydrogen, C independently of one another ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan; And

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

17., according to preparation method according to claim 16, is characterized in that, described Nonmetallocene part be selected from the compound with following chemical structural formula one or more:

18. according to preparation method according to claim 1, it is characterized in that, in the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene title complex for 1: 0.01-1, in the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part for 1: 0.0001-1, the ratio of described magnesium compound and described first solvent is 1mol: 75 ~ 400ml, in the mass ratio of the described magnesium compound of magnesium compound solid and described porous support for 1: 0.1-20, in the described magnesium compound of Mg element with the mol ratio of the described chemical processing agent of IVB race elemental metal for 1: 0.01-1, and in the described magnesium compound of Mg element and to help the mol ratio of chemical processing agent for 1: 0-1.0 described in Al element.

19. according to preparation method according to claim 1, it is characterized in that, described IVB race metallic compound be selected from IVB race metal halide, IVB race metal alkyl compound, IVB race metal alkoxide, IVB race metal alkyl halides and IVB race metal alkoxide halogenide one or more.

20., according to preparation method according to claim 19, is characterized in that, described IVB race metallic compound be selected from IVB race metal halide one or more.

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

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