CN102964480B

CN102964480B - Load type non-metallocene catalyst, its preparation method and application thereof

Info

Publication number: CN102964480B
Application number: CN201110259300.8A
Authority: CN
Inventors: 任鸿平; 李传峰; 左胜武; 阚林; 郭峰; 梅利; 柏基业; 陈韶辉
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: 2015-07-29
Anticipated expiration: 2031-08-31
Also published as: CN102964480A

Abstract

The present invention relates to a kind of load type non-metallocene catalyst and preparation method thereof.Described load type non-metallocene catalyst adopts precipitation magnesium compound and porous support, and after the mixed serum of solvent formation, and then obtain after convection drying after load non-metallocene metal complexes, its preparation method technique simple possible, the feature such as the charge capacity of Nonmetallocene title complex is adjustable.The invention still further relates to the application of described load type non-metallocene catalyst in alkene homopolymerization/copolymerization.Described application has and to have with prior art that catalysis in olefine polymerization promotor consumption is few, polymerization activity is higher, molecular weight distribution is narrower on year-on-year basis, copolymerization effect significantly, polymer stacks density is high, the high and feature such as adjustable of ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight prepared thus.

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, after the non cyclopentadienyl catalyst time appears at metallocene catalyst, be therefore otherwise known as " after luxuriant " olefin polymerization catalysis.It has the feature similar to metallocene catalyst, can customize polymkeric substance as required, and cost is lower.The central atom of non-metallocene catalyst includes nearly all transition metal, reaches, even exceed metallocene catalyst at some aspect of performance, becomes the olefin polymerization catalysis of new generation after Ziegler-Natta and metallocene catalyst.According to the difference of the central atom of Primary Catalysts, non-metallocene (IIIB race, IVB race, VB race, group vib, VIIB race) catalyzer and non-luxuriant rear transition metal (VIII) catalyzer can be divided into again further.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, high methylaluminoxane consumption, 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.

Existing olefin polymerization catalysis patent is mostly based on metallocene catalyst, as US 4808561, US 5240894, CN 1344749A, CN 1126480A, ZL94101358.8, CN 1307594A, CN 1103069A, CN1363537A, US6444604, EP0685494, US4871705 and EP0206794 etc., but these patents also all relate to and being carried on the carrier after process by the metallocene catalyst containing transition metal.

For the non-metallocene catalyst disclosed in patent ZL 01126323.7, ZL02151294.9ZL 02110844.7 and WO03/010207, patent CN 1539855A, CN 1539856A, CN 1789291A, CN 1789292A, CN 1789290A, WO/2006/063501, patent ZL200510119401.x etc. provide various ways and carry out load to obtain load type non-metallocene catalyst, but these patents all relate to and being carried on the carrier after process by the Nonmetallocene organic compound containing transition metal.

Chinese patent CN200910180602.9 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, obtains load type non-metallocene catalyst after drying.Patent 200910180605.2 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, adds precipitation agent precipitation, obtains load type non-metallocene catalyst after filtration washing drying.What these two kinds of methods adopted is magnesium compound carrier, and the particle form of catalyzer is difficult to control, and limits the morphology being polymerized thus and obtaining.

Load type non-metallocene catalyst preparation method disclosed in Chinese patent CN200910180603.3, CN200910180604.8, CN200910210989.8, CN200910210986.4, CN200910210985.X, CN200910210990.0 and above-mentioned patent similar, all use magnesium compound as carrier, the particle form that still there is catalyzer is difficult to control, and limits the morphology being polymerized thus and obtaining.

Be that the catalyzer of carrier demonstrates higher catalytic activity in olefin polymerization process with Magnesium Chloride Anhydrous, but this type of catalyzer is highly brittle, easily broken in polymerization reactor, thus cause polymer morphology bad.Silicon dioxide carried catalyzer has good mobility, can be used for gas fluidised bed polymerisation, but silicon dioxide carried metallocene and non-metallocene catalyst then show lower catalytic activity.If therefore magnesium chloride and silicon-dioxide are well organically combined, just may prepare and there is high catalytic activity, the catalyzer of the controlled and good abrasion strength resistance of globule size.

Such as CN1539856A discloses a kind of supported method of non-metallocene catalyst of composite carrier load, it is in accordance with the following steps: (1) using as carrier porous support 100-1000 DEG C, under inert atmosphere or reduced pressure, dry or roasting 1 ~ 24h carries out thermal activation; (2) be dissolved in by magnesium compound in tetrahydrofuran (THF)-ol mixed system and form solution, then join in this solution by the porosu solid of thermal activation, under 0 ~ 60 DEG C of agitation condition, fully reaction forms transparent system; Through filtration washing, drying and obtained complex carrier after draining; Or this clear solution is added non-polar organic solutions to make it to precipitate abundant precipitation, then obtained complex carrier is drained in filtration washing, drying; (3) non-metallocene olefin polymerization catalyst is dissolved in solvent, then with complex carrier or modify complex carrier contact 12 ~ 72 hours after filtration washing, drying drain into load type non-metallocene catalyst.This method needs first to prepare complex carrier, then contacts with catalyst solution.

CN1789290A discloses a kind of high activity loading method of load type non-metallocene catalyst, and it comprises the steps: carrier and chemical activating agent effect, obtains modifying carrier; Magnesium compound is dissolved in tetrahydrofuran (THF)-ol mixed system and forms solution, then modification carrier is joined in this solution react, wash after filtration, dry and drain obtained complex carrier; Be dissolved in by non-metallocene olefin polymerization catalyst in solvent, after then reacting with complex carrier, washing and filtering, drying are drained, obtained load type non-metallocene catalyst.This method first prepares modification carrier, then be obtained by reacting mixed carrier with magnesium compound, then contact with catalyst solution.

Patent CN101423574A discloses a kind of supported non-metallocene single site catalysis agent component and preparation method thereof, and the method comprises: the preparation of (1) magnesium chloride/silica-gel carrier; (2) preparation of alkylaluminoxane/magnesium chloride/silica-gel carrier and the preparation of (3) supported non-metallocene single site catalysts component.This method is also first prepare complex carrier, then reacts with alkylaluminoxane, finally contacts with catalyst solution.

EP260130 proposes loaded metallocene or non-luxuriant transition metal compound loaded on the silica supports of methylaluminoxane process, and non-luxuriant transition metal here only refers to ZrCl ₄, TiCl ₄or VOCl ₃, it is carrier surface through the mixture of organic-magnesium or magnesium compound and aluminum alkyls that this patent thinks optimum, but this process more complicated, need through many preparation processes.

Patent CN200610026765.8 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 this electron donor carry out process by adding in magnesium compound (as magnesium chloride)/tetrahydrofuran solution.

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

Patent CN200910180100.6 and CN200910180607.1 discloses not to be had under alcohol, Nonmetallocene title complex is dissolved in magnesium compound solution, then porous support is added, through the chemical processing agent process of IVB race after convection drying or filtration washing drying, thus obtain preparation method and the polymeric applications of load type non-metallocene catalyst, its Nonmetallocene title complex is present among carrier uniformly, but catalyzed ethylene polymerization activity is lower in an embodiment, and similarly load type non-metallocene catalyst preparation method and polymeric applications disclosed in patent CN200910180601.4 and CN200910180606.7, its essential difference is without the chemical processing agent process of IVB race, thus cause polymerization catalyst activity lower.

Patent CN200710162666.7 discloses loaded catalyst, load type non-metallocene catalyst and preparation method thereof, it is under having alcohol to exist, magnesium compound is dissolved in tetrahydrofuran solvent, add porous support, with titanium tetrachloride reaction after convection drying, last load non-metallocene metal complexes again, catalyst activity is higher, and be polymerized the polymkeric substance obtained thus and there is high bulk density, but preparation process is comparatively complicated, chemical processing agent and carrier reaction can destroy in type carrier structure, then produce fine polymer powder in the course of the polymerization process.

Even so, the ubiquitous problem of the load type non-metallocene catalyst existed in prior art is, supported process is complicated, load non-metallocene metal complexes again after generally needing to carry out the multi step strategy of carrier, olefin polymerizating activity low and be difficult to regulate, and in order to improve its polymerization activity, higher promotor consumption must be assisted when carrying out olefinic polymerization.

Therefore, still need a kind of load type non-metallocene catalyst, its preparation method is simple, is applicable to suitability for industrialized production, and can overcomes to prepare those problems existed in prior art load type non-metallocene catalyst process.

Summary of the invention

The present inventor finds through diligent research on the basis of existing technology, by using a kind of specific preparation method to manufacture described load type non-metallocene catalyst, just can 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 optionally to contact with described magnesium compound solution through the porous support of thermal activation treatment, obtain the step of the first mixed serum;

In described first mixed serum, add precipitation agent, obtain the step of complex carrier,

Nonmetallocene title complex is contacted with described 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, 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 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, 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, 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 the volume ratio of described precipitation agent and described first solvent is 1: 0.2 ~ 5, preferably 1: 0.5 ~ 2, more preferably 1: 0.8 ~ 1.5.

8. according to the preparation method described in any preceding aspect, it is characterized in that, described precipitation agent is selected from C _5-12alkane, C _5-12naphthenic hydrocarbon, halo C _1-10alkane and halo C _5-12one or more in naphthenic hydrocarbon, be preferably selected from pentane, hexane, heptane, octane, nonane, decane, hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane, methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three n-butyl bromide, chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, one or more in bromo cyclononane and bromo cyclodecane, be preferably selected from hexane further, heptane, one or more in decane and hexanaphthene, most preferably hexane.

9., according to the preparation method described in any preceding aspect, be also included in and make before described Nonmetallocene title complex contacts with described complex carrier, by the step helping complex carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

10. 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.

11., 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.

12. 1 kinds of load type non-metallocene catalysts, it manufactures by according to the preparation method described in any preceding aspect.

13. 1 kinds of alkene homopolymerization/copolymerization methods, it is characterized in that, with according to the load type non-metallocene catalyst described in aspect 12 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.

14. 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 is adjustable, can give full play to it obtains polyolefin product performance at catalysis in olefine polymerization.

In addition, by adopting different Nonmetallocene title complex consumptions, polymerization activity adjustable load type non-metallocene catalyst from low to high can be obtained, and the morphology obtained is better, bulk density is higher, molecular weight distribution is narrower, and when preparing ultrahigh molecular weight polyethylene(UHMWPE), polymkeric substance viscosity-average molecular weight is higher, adapts to different olefinic polymerization requirements thus.

Adopt method for preparing catalyst provided by the invention, the the second mixed serum mode containing Nonmetallocene title complex by convection drying due to load type non-metallocene catalyst obtains, therefore each component in catalyzer, the content comprising Nonmetallocene title complex is controllable.

Also find simultaneously, when the load type non-metallocene catalyst adopting the present invention to obtain and promotor form catalyst system, only need fewer promotor (such as methylaluminoxane or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity, molecular weight distribution is narrow, copolymerization time show significant comonomer effect, namely under relatively equal condition, Copolymerization activity is active higher than homopolymerization, and the polymkeric substance such as the polyethylene obtained by catalyzed alkene homopolymerization or copolymerization has excellent polymer morphology and high polymer bulk density.

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 optionally to contact with described magnesium compound solution through the porous support of thermal activation treatment, obtain the step of the first mixed serum; In described first mixed serum, add precipitation agent, obtain the step of complex carrier, Nonmetallocene title complex is contacted with described 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).

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 metering being added in described first solvent and carries out dissolving.

To the preparation time (i.e. the dissolution time of described magnesium compound) 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 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 an embodiment of the 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 period of element Table II A, 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, Grace 948, 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, in one embodiment, 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.

By making the described optional porous support through thermal activation contact (mixing) with described magnesium compound solution, obtain the first mixed serum thus.

According to the present invention, the mixing process of described porous support and described magnesium compound solution can adopt usual method to carry out, and there is no particular limitation.Such as can enumerate, under the preparation temperature of normal temperature to described magnesium compound solution, described porous support is metered in described magnesium compound solution, or in described porous support, be metered into described magnesium compound solution, mixing 0.1 ~ 8h, preferably 0.5 ~ 4h, optimum 1 ~ 2h (if desired by stirring).

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

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 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.

Then, by being metered into precipitation agent in described first mixed serum, solid matter being precipitated out from this mixed serum, namely obtaining complex carrier.

Below described precipitation agent is specifically described.

According to the present invention, term " precipitation agent " uses the common concept in this area, refers to and can reduce the solubleness of solid substance solute (such as described magnesium compound) in its solution and and then the unreactiveness liquid making it separate out in solid form from described solution.

According to the present invention, as described precipitation agent, such as can enumerate for solid substance solute (such as magnesium compound) to be precipitated is poor solvent, and for the described solvent for dissolving described solid substance solute (such as magnesium compound), be the solvent of good solvent, such as can enumerate C _5-12alkane, C _5-12naphthenic hydrocarbon, halo C _1-10alkane and halo C _5-12naphthenic hydrocarbon.

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

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

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

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

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

The feed postition of precipitation agent can add for disposable or drip, and preferably disposablely adds.In this precipitation process, the dispersion of stirring and promoting precipitation agent can be utilized, and be conducive to the final precipitation of solid product.This stirring can adopt any form (such as stirring rake), and rotating speed is generally 10 ~ 1000 revs/min etc.

To the temperature of described precipitation agent, also there is no particular limitation, but general preferred normal temperature is to the temperature (preferred 20-80 DEG C, more preferably 40-60 DEG C) of the boiling point lower than used any solvent and precipitation agent, but be sometimes not limited to this.And, this precipitation process general also preferred at normal temperature to temperature (the preferred 20-80 DEG C of the boiling point lower than used any solvent and precipitation agent, more preferably 40-60 DEG C) under carry out 0.3-12 hour, but be sometimes not limited to this, and with solid product substantially completely precipitation be as the criterion.

Completely after precipitation, obtained solid product filtered, wash and drying, obtain described complex carrier thus.

Method for described filtration, washing and drying is not particularly limited, this area routine can be used as required to use those.As required, described washing generally carries out 1 ~ 6 time, preferably 3 ~ 4 times.Wherein, washer solvent preferably uses the solvent identical with precipitation agent, but also can be different.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.Time of drying is generally 2-20 hour, but also can be different for the solvent case dissolving described magnesium compound according to what specifically use.Such as, when adopting tetrahydrofuran (THF) as solvent for dissolving described magnesium compound, drying temperature is generally about 80 DEG C, dry 2 ~ 12 hours under vacuo, and when adopting toluene as solvent for dissolving described magnesium compound, drying temperature is generally about 100 DEG C, dry 4 ~ 24 hours under vacuo.

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.

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

When manufacturing described second mixed serum, to the way of contact and engagement sequence etc. of described complex carrier and described Nonmetallocene title complex (and described second solvent), there is no particular limitation, such as can enumerate and described complex carrier is first mixed with described Nonmetallocene title complex, and then add the scheme of described second solvent wherein; Or make described Nonmetallocene title complex be dissolved in described second solvent, manufacture Nonmetallocene complex solution thus, and then the scheme that described complex carrier is mixed with described Nonmetallocene complex 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 complex carrier and the contact reacts of described Nonmetallocene title complex 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 title complex solvent), there is no particular limitation, as long as it can dissolve described Nonmetallocene title complex.As described second solvent, such as C can be enumerated _6-12aromatic hydrocarbon, halo C _6-12aromatic hydrocarbon, halo C _1-10one or more in alkane, 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, methylene dichloride and tetrahydrofuran (THF).

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

When manufacturing described second mixed serum or described Nonmetallocene complex 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 complex carrier fully contacts with described Nonmetallocene title complex.Such as, easily, described Nonmetallocene title complex is generally 0.01 ~ 0.25 grams per milliliter relative to the ratio of described second solvent, preferably 0.05 ~ 0.16 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 Nonmetallocene title complex contacts with described complex carrier, 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.

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.

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 make describedly to contact under the existence of the second solvent with described Nonmetallocene title complex through pretreated complex carrier according to aforementioned identical mode, just described complex carrier is replaced with described through pretreated complex carrier.

That is, according to describe entirely identical mode before and carry out described contact reacts, just described complex carrier is replaced with described through pretreated complex carrier, and similarly obtains described second mixed serum.

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 the described solvent for dissolving described magnesium compound, described magnesium compound (solid) is made to reach 1mol: 75 ~ 400ml, preferred 1mol: 150 ~ 300ml, more preferably 1mol: 200 ~ 250ml with the ratio of described solvent.

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, preferably 1: 0.5-10, more preferably 1: 1-5.

According to the present invention, as the consumption of described precipitation agent, the volume ratio of described precipitation agent and the described solvent for dissolving described magnesium compound is made to be 1: 0.2 ~ 5, preferably 1: 0.5 ~ 2, more preferably 1: 0.8 ~ 1.5.

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.

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

Al(R) ₃(III)

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, the compound shown in following general formula (IV) such as can be enumerated:

Al(R) _nX _3-n(IV)

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 STM D4020-00, (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 the first solvent adopts tetrahydrofuran (THF), and porous support adopts silicon-dioxide, i.e. silica gel, and model is the ES757 of Ineos company, before use by silica gel 600 DEG C, continue roasting 4h and thermal activation under nitrogen atmosphere.Precipitation agent adopts hexane, and Nonmetallocene title complex employing structure is compound, second solvent adopt methylene dichloride.

Take 5g Magnesium Chloride Anhydrous, dissolve completely under normal temperature after adding the first solvent, obtain magnesium compound solution, then add the silica gel through thermal activation, stir under normal temperature after 2 hours and form the first mixed serum.Be added drop-wise to by precipitation agent in the first mixed serum, at 60 DEG C, stirring reaction makes it to precipitate completely for 4 hours, and filter, precipitation agent washs 2 times, and each precipitation agent consumption is 60ml, vacuumizes drying, obtain complex carrier at being uniformly heated to 60 DEG C.

Then added by complex carrier in the solution that Nonmetallocene title complex and the second solvent formed, stirring reaction 6 hours, forms the second mixed serum at normal temperatures, and under last normal temperature, vacuum-drying obtains load type non-metallocene catalyst.

Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 210ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.08; The mass ratio of magnesium compound and porous support is 1: 2; Precipitation agent and the first solvent volume proportioning are 1: 1.

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

Embodiment 1-1

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

Porous support changes into 955 of Grace company, 400 DEG C, continue roasting 8h and thermal activation under nitrogen atmosphere.

Toluene changed into by first solvent, and precipitation agent changes hexanaphthene into, and Nonmetallocene title complex adopts toluene changed into by second solvent.

Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 150ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.15; The mass ratio of magnesium compound and porous support is 1: 4; Precipitation agent and the first solvent volume proportioning are 1: 2.

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

Embodiment 1-2

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

Porous support adopts aluminium sesquioxide.By aluminium sesquioxide 700 DEG C, continue roasting 6h under nitrogen atmosphere.

Magnesium compound changes into anhydrous magnesium bromide (MgBr ₂), Nonmetallocene title complex adopts ethylbenzene changed into by first solvent, and heptane changed into by precipitation agent, and the second solvent adopts tetrahydrofuran (THF).

Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 250ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.20; The mass ratio of magnesium compound and porous support is 1: 1; Precipitation agent and the first solvent volume proportioning are 1: 0.7.

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

Embodiment 1-3

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

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.

Magnesium compound changes into oxyethyl group magnesium chloride (MgCl (OC ₂h ₅)), Nonmetallocene title complex adopts dimethylbenzene changed into by first solvent, and decane changed into by precipitation agent.

Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 300ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.04; The mass ratio of magnesium compound and porous support is 1: 3; Precipitation agent and the first solvent volume proportioning are 1: 1.5.

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

Embodiment 1-4

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

Porous support adopts polynite.By polynite 400 DEG C, continue roasting 8h under nitrogen atmosphere.

Magnesium compound changes into magnesium ethylate (Mg (OC ₂h ₅) ₂), Nonmetallocene title complex adopts diethylbenzene changed into by first solvent, and pentane changed into by precipitation agent.

Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 400ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.30; The mass ratio of magnesium compound and porous support is 1: 5; Precipitation agent and the first solvent volume proportioning are 1: 0.5.

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

Embodiment 1-5

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

Porous support adopts the polystyrene of partial cross-linked (degree of crosslinking is 30%).By this polystyrene 100 DEG C, continue under nitrogen atmosphere to dry 12h.

Magnesium compound changes into methylmagnesium-chloride (Mg (CH ₃) Cl), Nonmetallocene title complex adopts chlorotoluene changed into by first solvent.

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

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

Embodiment 1-6

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

Porous support adopts diatomite.By diatomite 500 DEG C, continue roasting 8h under nitrogen atmosphere.

Magnesium compound changes into ethylmagnesium chloride (Mg (C ₂h ₅) Cl), bromo ethylbenzene changed into by the first solvent, and Nonmetallocene title complex adopts suberane changed into by precipitation agent.

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

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

Embodiment 1-7

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

Porous support adopts titanium dioxide.By titanium dioxide 300 DEG C, continue roasting 6h under nitrogen atmosphere.

Magnesium compound changes into magnesium ethide (Mg (C ₂h ₅) ₂), Nonmetallocene title complex adopts

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

Embodiment 1-8

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

Magnesium compound changes into methyl ethoxy magnesium (Mg (OC ₂h ₅) (CH ₃)), chlorocyclohexane changed into by precipitation agent.

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

Embodiment 1-9

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

Magnesium compound changes into butyl magnesium ethylate (Mg (OC ₂h ₅) (C ₄h ₉)), bromo suberane changed into by precipitation agent.

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

Embodiment 2

Magnesium compound adopts Magnesium Chloride Anhydrous, and the first solvent adopts tetrahydrofuran (THF), and porous support adopts silicon-dioxide, i.e. silica gel, and model is the ES757 of Ineos company, before use by silica gel 600 DEG C, continue roasting 4h and thermal activation under nitrogen atmosphere.Precipitation agent adopts hexane, helps chemical processing agent to adopt triethyl aluminum, and Nonmetallocene title complex employing structure is compound, second solvent adopt methylene dichloride.

Take 5g Magnesium Chloride Anhydrous, dissolve completely under normal temperature after adding the first solvent, obtain magnesium compound solution, then add the silica gel through thermal activation, stir and form the first mixed serum after 2 hours, then drip precipitation agent in the first mixed serum, at 60 DEG C, stirring reaction makes it to precipitate completely for 4 hours, filters, precipitation agent washs 2 times, each precipitation agent consumption is 60ml, vacuumizes drying, obtain complex carrier at being uniformly heated to 60 DEG C.

Then in obtained complex carrier, 60ml hexane is added, triethyl aluminum (concentration is the hexane solution of 15wt%) is adopted to help chemical processing agent process complex carrier under agitation, triethyl aluminum is dripped with 30 minutes, at 60 DEG C, stirring reaction is after 4 hours, filter, hexanes wash 2 times, each hexane consumption 60ml, under normal temperature, vacuum-drying obtains pretreated complex carrier.

Then added by pretreated complex carrier in the solution that Nonmetallocene title complex and the second solvent formed, stirring reaction formed the second mixed serum after 6 hours at normal temperatures, and under last normal temperature, vacuum-drying obtains load type non-metallocene catalyst.

Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 210ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.08; The mass ratio of magnesium compound and porous support is 1: 2; Precipitation agent and the first solvent volume proportioning are 1: 1; Magnesium compound with help chemical processing agent mol ratio for 1: 0.15 in Al element.

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

Embodiment 2-1

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

Toluene changed into by first solvent, and precipitation agent changes hexanaphthene into, helps chemical processing agent to change into methylaluminoxane (toluene solution of MAO, 10wt%), and Nonmetallocene title complex adopts toluene changed into by second solvent.

Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 150ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.15; The mass ratio of magnesium compound and porous support is 1: 4; Precipitation agent and the first solvent volume proportioning are 1: 2; Magnesium compound with help chemical processing agent mol ratio for 1: 0.20 in Al element.

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

Embodiment 2-2

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

Magnesium compound changes into anhydrous magnesium bromide (MgBr ₂), Nonmetallocene title complex adopts ethylbenzene changed into by first solvent, and heptane changed into by precipitation agent, helps chemical processing agent to change into trimethyl aluminium (Al (CH ₃) ₃), tetrahydrofuran (THF) changed into by the second solvent.

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

Embodiment 2-3

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

Magnesium compound changes into oxyethyl group magnesium chloride (MgCl (OC ₂h ₅)), Nonmetallocene title complex adopts dimethylbenzene changed into by first solvent, and decane changed into by precipitation agent, helps chemical processing agent to change into triisobutyl aluminium (Al (i-C ₄h ₉) ₃).

Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 300ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.04; The mass ratio of magnesium compound and porous support is 1: 3; Precipitation agent and the first solvent volume proportioning are 1: 1.5; Magnesium compound with help chemical processing agent mol ratio for 1: 0.05 in Al element.

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

Embodiment 2-4

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

Magnesium compound changes into magnesium ethylate (Mg (OC ₂h ₅) ₂), Nonmetallocene title complex adopts diethylbenzene changed into by first solvent, and pentane changed into by precipitation agent, helps chemical processing agent to change into isobutyl aluminium alkoxide.

Wherein proportioning is, magnesium compound and the first solvent burden ratio are 1mol: 400ml; Magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.30; The mass ratio of magnesium compound and porous support is 1: 5; Precipitation agent and the first solvent volume proportioning are 1: 0.5; Magnesium compound with help chemical processing agent mol ratio for 1: 0.50 in Al element.

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

Embodiment 2-5

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

Wherein proportioning is, magnesium compound and Nonmetallocene title complex mol ratio are 1: 0.10; The mass ratio of magnesium compound and porous support is 1: 10; Magnesium compound with help chemical processing agent mol ratio for 1: 0.40 in Al element.

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

Comparative example A

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

Magnesium compound and Nonmetallocene title complex mol ratio change into 1: 0.16;

Catalyzer is designated as CAT-A.

Comparative example B

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

Magnesium compound and Nonmetallocene title complex mol ratio change into 1: 0.04;

Catalyzer is designated as CAT-B.

Comparative example C

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

Magnesium compound solution is directly vacuumized drying and obtains by complex carrier use at normal temperatures.

Catalyzer is designated as CAT-C.

Embodiment 3 (Application Example)

By the catalyzer CAT-1 ~ CAT-2 obtained in the embodiment of the present invention, CAT-1-1 ~ 9, CAT-2-1 ~ 5, CAT-A ~ C, the homopolymerization carrying out ethene respectively under the following conditions in accordance with the following methods, copolymerization with prepare ultrahigh molecular weight polyethylene(UHMWPE).

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 50mg 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 50mg 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.

Known by the test-results data of sequence number in table 13 and 4,16 and 17, 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.

And visible by the molecular weight distribution of sequence number 1 to 4 and 14 to 17 in table 1, narrower by the molecular weight distribution obtained after catalyst olefinic polymerization provided by the invention.It is well known in the art that adopt Ziegler-Natta catalyst (active centre the is IVB race metal titanium) molecular weight distribution prepared between 5 ~ 8, and adopt molecular weight distribution prepared by chromium system Ziegler-Natta catalyst between 8 ~ 15.

In contrast table 1, the test-results data of sequence number 1 and 3, sequence number 14 and 16 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.

Known by the test-results data of sequence number 1 and comparative example sequence number 23 ~ 24 in contrast table 1, increase or reduce the add-on of Nonmetallocene title complex in catalyzer, its activity increases thereupon or reduces.But polymer stacks density decreases, thus illustrate that Nonmetallocene title complex has the effect determining catalyst activity, and take into account catalyst activity and polymer stacks density, the add-on of Nonmetallocene title complex is not more high better.

Sequence number 1 and 25 in contrast table 1, in table 2, sequence number 1 and 7 is visible, in catalyst preparation process, complex carrier adopts the load type non-metallocene catalyst that the magnesium compound solution precipitator method obtain, the load type non-metallocene catalyst that polymer stacks density adopts magnesium compound solution direct drying method to obtain higher than complex carrier when catalysis in olefine polymerization, that is understands that the morphology adopting load type non-metallocene catalyst preparation method provided by the invention to obtain is better.

From table 2, adopt catalyzer provided by the present invention, ultrahigh molecular weight polyethylene(UHMWPE) can be prepared, its bulk density increases all to some extent, and it is contrast sequence number 1 and 2,3 and 4 visible, adopt methylaluminoxane can increase catalysis in olefine polymerization activity as promotor, and the viscosity-average molecular weight of ultrahigh molecular weight polyethylene(UHMWPE).In contrast table 2, the test-results data of sequence number 1 and comparative example 5 and 6 are known, and increase in catalyzer or reduce metallocene complex add-on, polymkeric substance viscosity-average molecular weight reduces thereupon or increases.Thus illustrate that Nonmetallocene title complex also has the effect increasing polymkeric substance viscosity-average molecular weight.

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 said preparation method is optionally also included in and makes before described Nonmetallocene title complex contacts with described complex carrier, 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;

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 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 or C ₈-C ₃₀condensed ring radical;

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 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,

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, 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, 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 and to help the mol ratio of chemical processing agent for 1: 0-1.0 described in Al element, and the volume ratio of described precipitation agent and described first solvent is 1: 0.2 ~ 5.

14., according to preparation method according to claim 1, is characterized in that, described precipitation agent is selected from C _5-12alkane, C _5-12naphthenic hydrocarbon, halo C _1-10alkane and halo C _5-12one or more in naphthenic hydrocarbon.

15. 1 kinds of load type non-metallocene catalysts, it manufactures by according to the preparation method described in any one of claim 1-14.

16. 1 kinds of alkene homopolymerization/copolymerization methods, it is characterized in that, with according to load type non-metallocene catalyst according to claim 15 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.