CN102964475B

CN102964475B - Supported non-metallocene catalyst, preparation method and application

Info

Publication number: CN102964475B
Application number: CN201110259282.3A
Authority: CN
Inventors: 李传峰; 任鸿平; 陈韶辉; 阚林; 郭峰; 左胜武; 梅利; 柏基业
Original assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Priority date: 2011-08-31
Filing date: 2011-08-31
Publication date: 2014-12-10
Anticipated expiration: 2031-08-31
Also published as: CN102964475A

Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method. The supported non-metallocene catalyst is prepared by the steps of using a porous carrier to add in a magnesium compound solution to form a mixed slurry, loading on a non-metallocene complex and precipitating by a precipitating agent, filtering, washing and drying. The preparation method is simple and feasible, and the load capacity of the non-metallocene ligand is adjustable. The invention also relates to the application of the supported non-metallocene catalyst in olefin homopolymerisation/copolymerization. Compared with the prior art, the supported non-metallocene catalyst has the characteristics of less usage of a cocatalyst for catalyzing polymerization of alkene, high polymerization activity, narrow molecular weight distribution, substantial copolymerization effect, high bulk density of polymer, and high and adjustable viscosity average molecular weight of the prepared ultrahigh molecular weight polyethylene.

Description

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

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

Technical field

The present invention relates to a kind of non-metallocene catalyst.Particularly, the present invention relates to a kind of load type non-metallocene catalyst, its preparation method and the application in alkene homopolymerization/copolymerization thereof.

Background technology

The non-metallocene catalyst that middle and later periods nineteen nineties occurs, " after luxuriant " olefin polymerization catalysis after appearing at metallocene catalyst on the non cyclopentadienyl catalyst time, is therefore otherwise known as.It has the feature similar to metallocene catalyst, can customize as required polymkeric substance, and cost is lower.The central atom of non-metallocene catalyst has comprised nearly all transition metal, reaches at some aspect of performance, even exceedes metallocene catalyst, 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, further can divide into again non-metallocene (IIIB family, IVB family, VB family, group vib, VIIB family) catalyzer and non-luxuriant rear transition metal (VIII family) catalyzer.By the excellent property of the polyolefin products of such catalyzer manufacturing, and low cost of manufacture.Non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and there is cis alkyl or halogen metal division center, easily carry out alkene insertion and σ-key and shift, the easy alkylation of central metal, is conducive to the generation at cation activity center; The title complex forming has the geometric configuration of restriction, stereoselectivity, electronegativity and chirality controllability, and in addition, the metal-carbon key forming easily polarizes, and is more conducive to polymerization and the copolymerization of alkene.Therefore, even if also can obtain the olefin polymer of higher molecular weight 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/catalyst for copolymerization or catalyst system, there is alkene homopolymerization/copolymerization performance widely, but need higher promotor consumption during in olefinic polymerization at the disclosed catalyzer of this patent or catalyst system, could obtain suitable olefin polymerizating activity, and it is short to exist active duration in polymerization process, the phenomenons such as the sticky still of polymkeric substance.

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

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 the metallocene catalyst that contains transition metal are carried on carrier after treatment.

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

Chinese patent CN200910180602.9 discloses a kind of preparation method of load type non-metallocene catalyst, and it is that magnesium compound and Nonmetallocene title complex are dissolved in solvent, after being dried, obtains load type non-metallocene catalyst.Patent 200910180605.2 discloses a kind of preparation method of load type non-metallocene catalyst, and it is that magnesium compound and Nonmetallocene title complex are dissolved in solvent, adds precipitation agent precipitation, after filtration washing is dry, obtains load type non-metallocene catalyst.What these two kinds of methods adopted is magnesium compound carrier, and the particle form of catalyzer is difficult to control, and has limited the morphology that polymerization obtains thus.

Chinese patent CN200910180603.3, CN200910180604.8, CN200910210989.8, CN200910210986.4, the disclosed load type non-metallocene catalyst preparation method of CN200910210985.X, CN200910210990.0 and above-mentioned patent are similar, what all use is that magnesium compound is as carrier, still exist the particle form of catalyzer to be difficult to control, limited the morphology that polymerization obtains thus.

Catalyzer taking Magnesium Chloride Anhydrous as carrier demonstrates higher catalytic activity in olefin polymerization process, but this type of catalyzer is highly brittle, easily broken in polymerization reactor, thereby causes 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 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 load method of non-metallocene catalyst of composite carrier load, it is in accordance with the following steps: (1) using as the porous support of carrier under 100-1000 DEG C, inert atmosphere or reduced pressure, dry or roasting 1～24h carries out thermal activation; (2) magnesium compound is dissolved in tetrahydrofuran (THF)-ol mixed system and forms solution, then the porosu solid of thermal activation is joined in this solution, under 0～60 DEG C of agitation condition, fully reaction forms transparent system; Through filtration washing, dry and drain after make complex carrier; Or add non-polar organic solutions to make it precipitation this clear solution and fully separate out, then filtration washing, dry draining make complex carrier; (3) non-metallocene olefin polymerization catalyst is dissolved in solvent, then filtration washing with complex carrier or after modifying complex carrier and contact 12～72 hours, be dried and drain into load type non-metallocene catalyst.This method need to first be prepared 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:, by carrier and chemical activating agent effect, to obtain modifying carrier; Magnesium compound is dissolved in tetrahydrofuran (THF)-ol mixed system and forms solution, then modification carrier is joined in this solution and reacted, wash after filtration, dry and drain and make complex carrier; Non-metallocene olefin polymerization catalyst is dissolved in solvent, and after then reacting with complex carrier, washing and filtering, dry draining, make load type non-metallocene catalyst.This method is first to prepare modification carrier, then reacts and obtain mixed carrier with magnesium compound, then contacts 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 the preparation of alkylaluminoxane/magnesium chloride/silica-gel carrier and (3) supported non-metallocene single site catalysts component.This method is also first to 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 processing, and the non-luxuriant transition metal here only refers to ZrCl ₄, TiCl ₄or VOCl ₃, what this patent was thought optimum is the mixture of carrier surface through organic-magnesium or magnesium compound and aluminum alkyls, but this process more complicated need to be passed through many preparation processes.

Patent CN200610026765.8 discloses a class single active center Z-N olefin polymerization catalysis.This catalyzer is using the salicylic alidehyde imine derivative of the salicylic alidehyde imine that contains coordinating group or replacement as electron donor, by adding after pretreated carrier (as silica gel), metallic compound (as titanium tetrachloride) and this electron donor are processed and obtain 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 disclose not to be had under alcohol, Nonmetallocene title complex is dissolved in magnesium compound solution, then add porous support, after convection drying or filtration washing are dry through the chemical processing agent processing of IVB family, thereby 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 patent CN200910180601.4 and the disclosed load type non-metallocene catalyst preparation method of CN200910180606.7 and polymeric applications, its main difference is the chemical processing agent processing without IVB family, thereby cause polymerization catalyst activity lower.

Patent CN200710162666.7 discloses loaded catalyst, load type non-metallocene catalyst and preparation method thereof, it is to have under alcohol existence, magnesium compound is dissolved in tetrahydrofuran solvent, add porous support, after convection drying with titanium tetrachloride reaction, finally load non-metallocene metal complexes again, catalyst activity is higher, and the polymkeric substance that polymerization obtains thus has high bulk density, but preparation process is comparatively complicated, chemical processing agent reacts with carrier and can destroy in type carrier structure, then in polymerization process, produces fine polymer powder.

Even so, the ubiquitous problem of load type non-metallocene catalyst existing in prior art is, load process complexity, generally need to carry out the multistep of carrier and process afterwards load non-metallocene metal complexes again, olefin polymerizating activity low and be difficult to regulate, and in order to improve its polymerization activity, in the time carrying out olefinic polymerization, must assist higher promotor consumption.

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 that exist in prior art load type non-metallocene catalyst process.

Summary of the invention

The inventor finds through diligent research on the basis of existing technology, by manufacturing described load type non-metallocene catalyst by a kind of specific preparation method, just can solve foregoing problems, and complete thus the present invention.

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

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

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

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

The optionally porous support through thermal activation treatment is contacted with described magnesium compound solution, obtain the step of the first mixed serum;

Nonmetallocene title complex is contacted with described the first mixed serum, obtain the step of the second mixed serum; With

In described the second mixed serum, add precipitation agent, obtain the step of described load type non-metallocene catalyst.

2. according to the preparation method described in aforementioned either side, it is characterized in that, described porous support is selected from olefin homo or multipolymer, polyvinyl alcohol or its multipolymer, cyclodextrin, polyester or copolyesters, polymeric amide or copolyamide, ryuron or multipolymer, Voncoat R 3310 or multipolymer, methacrylic acid ester homopolymer or multipolymer, styrene homopolymers or multipolymer, the partial cross-linked form of these homopolymer or multipolymer, periodic table of elements IIA, IIIA, the refractory oxide of IVA or IVB family 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 be selected from silicon-dioxide.

3. according to the preparation method described in aforementioned either side, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium, be preferably selected from one or more in magnesium halide, more preferably magnesium chloride.

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

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

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

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

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from periodic table of elements III-th family to XI family atoms metal, preferably IVB family atoms metal, more preferably Ti (IV) and Zr (IV);

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

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

A be selected from Sauerstoffatom, sulphur atom, selenium atom, -NR ²³r ²⁴,-N (O) R ²⁵r ²⁶, -PR ²⁸r ²⁹,-P (O) R ³⁰oR ³¹, sulfuryl, sulfoxide group or-Se (O) R ³⁹, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

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 the P coordination atom of respectively doing for oneself;

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 the P coordination atom of respectively doing for oneself;

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 the P coordination atom of respectively doing for oneself;

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

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

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

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

R ⁵be selected from lone-pair electron on nitrogen, hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R ⁵during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, R ⁵in N, O, S, P and Se can be used as coordination atom and described center IVB family atoms metal carries out coordination,

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

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

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

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

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

Described nitrogen-containing group is selected from -NR ²³r ²⁴,-T-NR ²³r ²⁴or-N (O) R ²⁵r ²⁶;

Described phosphorus-containing groups is selected from -PR ²⁸r ²⁹,-P (O) R ³⁰r ³¹or-P (O) R ³²(OR ³³);

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

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

Described containing be selected from-SeR of seleno group ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹or-T-Se (O) R ³⁹;

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

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

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

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

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

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

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

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

Described containing be selected from-SnR of tin group ⁵⁰r ⁵¹r ⁵²,-T-SnR ⁵³or-T-Sn (O) R ⁵⁴,

Described Ar represents C ₆-C ₃₀aryl, and

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

Described group T defines with aforementioned either side.

7. according to the preparation method described in aforementioned either side, 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, further be preferably selected from hexane, heptane, one or more in decane and hexanaphthene, most preferably hexane.

8. according to the preparation method described in aforementioned either side, it is characterized in that, taking the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene title complex as 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 solvent is 1mol: 75～400ml, preferably 1mol: 150～300ml, more preferably 1mol: 200～250ml, taking the described magnesium compound of magnesium compound solid and the mass ratio of described porous support as 1: 0.1-20, preferably 1: 0.5-10, more preferably 1: 1-5, and the volume ratio of described precipitation agent and described solvent is 1: 0.2～5, preferably 1: 0.5～2, more preferably 1: 0.8～1.5.

9. a load type non-metallocene catalyst, it is to be manufactured by the preparation method according to described in aforementioned either side.

10. an alkene homopolymerization/copolymerization process, it is characterized in that, taking the load type non-metallocene catalyst according to described in aspect 9 as 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 as promotor, make alkene homopolymerization or copolymerization.

11. 1 kinds of alkene homopolymerization/copolymerization process, is characterized in that, comprise the following steps:

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

Taking described load type non-metallocene catalyst as 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 as promotor, make alkene homopolymerization or copolymerization.

Technique effect

Preparation method's technique simple possible of load type non-metallocene catalyst of the present invention, and the charge capacity of Nonmetallocene title complex is adjustable, can give full play to it obtains polyolefin product performance at catalysis in olefine polymerization, thereby and can regulate polymer performance and ultrahigh molecular weight polyethylene(UHMWPE) viscosity-average molecular weight by the difference that regulates add-on.

In addition, by adopting different Nonmetallocene title complex consumptions, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst adapts to different olefinic polymerization requirements thus.

Adopt method for preparing catalyst provided by the invention, because load type non-metallocene catalyst is to obtain by mixed serum the filtration drying mode of precipitation magnesium-containing compound, porous support, Nonmetallocene title complex and solvent, therefore in catalyzer, each component is in conjunction with tight, and the polymer stacks density obtaining is thus higher.

Also find simultaneously, when the load type non-metallocene catalyst that employing the present invention obtains 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, show significant comonomer effect when copolymerization, under relatively equal condition, Copolymerization activity is higher than homopolymerization activity, and the polymkeric substance such as the polyethylene obtaining by catalyzed alkene homopolymerization or copolymerization has good polymer morphology and high polymer bulk density.

Embodiment

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

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

The preparation method who the present invention relates to a kind of load type non-metallocene catalyst, comprises the following steps: magnesium compound is dissolved in solvent, obtains the step of magnesium compound solution; The optionally porous support through thermal activation treatment is contacted with described magnesium compound solution, obtain the step of the first mixed serum; Nonmetallocene title complex is contacted with described the first mixed serum, obtain the step of the second mixed serum; With in described the second mixed serum, add precipitation agent, 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 conventional organic or inorganic solid water-free magnesium-containing compound using of carrier as supported olefin polymerization catalyst.

According to the present invention, as described magnesium compound, such as enumerating magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and alkyl alkoxy magnesium.

Particularly, as described magnesium halide, such as enumerating magnesium chloride (MgCl ₂), magnesium bromide (MgBr ₂), magnesium iodide (MgI ₂) and magnesium fluoride (MgF ₂) etc., wherein preferred magnesium chloride.

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

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

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

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

As described alkyl alkoxy magnesium, such as enumerating methyl methoxy base magnesium (Mg (OCH ₃) (CH ₃)), methyl ethoxy magnesium (Mg (OC ₂h ₅) (CH ₃)), methyl propoxy-magnesium (Mg (OC ₃h ₇) (CH ₃)), methyl n-butoxy magnesium (Mg (OC ₄h ₉) (CH ₃)), methyl isobutoxy magnesium (Mg (i-OC ₄h ₉) (CH ₃)), ethyl magnesium methylate (Mg (OCH ₃) (C ₂h ₅)), ethyl magnesium ethylate (Mg (OC ₂h ₅) (C ₂h ₅)), ethyl propoxy-magnesium (Mg (OC ₃h ₇) (C ₂h ₅)), ethyl n-butoxy magnesium (Mg (OC ₄h ₉) (C ₂h ₅)), ethyl isobutoxy magnesium (Mg (i-OC ₄h ₉) (C ₂h ₅)), propyl group magnesium methylate (Mg (OCH ₃) (C ₃h ₇)), propyl group magnesium ethylate (Mg (OC ₂h ₅) (C ₃h ₇)), propyl group propoxy-magnesium (Mg (OC ₃h ₇) (C ₃h ₇)), propyl group n-butoxy magnesium (Mg (OC ₄h ₉) (C ₃h ₇)), propyl group isobutoxy magnesium (Mg (i-OC ₄h ₉) (C ₃h ₇)), normal-butyl magnesium methylate (Mg (OCH ₃) (C ₄h ₉)), normal-butyl magnesium ethylate (Mg (OC ₂h ₅) (C ₄h ₉)), normal-butyl propoxy-magnesium (Mg (OC ₃h ₇) (C ₄h ₉)), normal-butyl n-butoxy magnesium (Mg (OC ₄h ₉) (C ₄h ₉)), normal-butyl isobutoxy magnesium (Mg (i-OC ₄h ₉) (C ₄h ₉)), isobutyl-magnesium methylate (Mg (OCH ₃) (i-C ₄h ₉)), isobutyl-magnesium ethylate (Mg (OC ₂h ₅) (i-C ₄h ₉)), isobutyl-propoxy-magnesium (Mg (OC ₃h ₇) (i-C ₄h ₉)), isobutyl-n-butoxy magnesium (Mg (OC ₄h ₉) (i-C ₄h ₉)) and isobutyl-isobutoxy magnesium (Mg (i-OC ₄h ₉) (i-C ₄h ₉)) etc., wherein preferred butyl magnesium ethylate.

These magnesium compounds can use separately one, also can multiple mixing use, not special restriction.

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

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

Below the step that obtains described magnesium compound solution is specifically described.

Particularly, make described magnesium compound (solid) be dissolved in suitable solvent (being sometimes referred to as below the solvent for dissolving described magnesium compound), thereby obtain described magnesium compound solution.

As described solvent, such as enumerating C _6-12aromatic hydrocarbon, halo C _6-12aromatic hydrocarbon, ester and ether equal solvent.

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

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

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

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

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

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

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

These solvents can use separately one, also can use with the multiple mixing of ratio arbitrarily.

In order to prepare described magnesium compound solution, the meterings such as described magnesium compound are added in described solvent and dissolved.

There is no particular limitation for preparation time (being the dissolution time of described magnesium compound etc.) to described magnesium compound solution, but be generally 0.5～24h, preferably 4～24h.In this preparation process, can utilize and stir the dissolving that promotes described magnesium compound etc.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, such as can enumerate this area manufacturing when supported olefin polymerization catalyst as carrier conventional those organic or inorganic porosu solids that use.

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

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

According to an embodiment of the invention, before use described Porous-Organic solid is carried out to thermal activation treatment.This thermal activation treatment can be carried out according to common mode, such as under reduced pressure or under inert atmosphere, described Porous-Organic solid being carried out to heat treated.Here said inert atmosphere refer in gas, only contain extremely trace or do not contain can with the component of described Porous-Organic solid reaction.As described inert atmosphere, such as enumerating nitrogen or rare gas atmosphere, preferred nitrogen atmosphere.Due to the poor heat resistance of Porous-Organic solid, therefore this thermal activation process is not to destroy the structure of described Porous-Organic solid itself and to basic composition is prerequisite.Usually, the temperature of this thermal activation is 50～400 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 need to save backup in malleation under inert atmosphere.

As described inorganic porous solid, such as enumerating the refractory oxide (such as silicon-dioxide (being called again silicon oxide or silica gel), aluminum oxide, magnesium oxide, titanium oxide, zirconium white or Thorotrast etc.) of periodic table of elements IIA, IIIA, IVA or IVB family metal, or any infusibility composite oxides of these metals (such as oxidation sial, oxidation magnalium, titanium oxide silicon, titanium oxide magnesium and titanium oxide aluminium etc.), and clay, molecular sieve (such as ZSM-5 and MCM-41), mica, polynite, wilkinite and diatomite etc.As described inorganic porous solid, can also enumerate the oxide compound being generated by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound, such as the silica gel being obtained by silicon tetrachloride pyrohydrolysis, or the aluminum oxide being obtained by aluminum chloride pyrohydrolysis etc.

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

According to the present invention, suitable silicon-dioxide can be manufactured by ordinary method, or can be the commerical prod that can buy arbitrarily, such as enumerating Grace 955, Grace 948, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245 and the Aerosil812 of Grace company, ES70, ES70X, ES70Y, ES70W, ES757, EP10X and the EP11 of Ineos company, and the CS-2133 of Pq Corp. and MS-3040.

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

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

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

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

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

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 enumerating, at normal temperature under the preparation temperature of described magnesium compound solution, in described magnesium compound solution, be metered into described porous support, or be metered into described magnesium compound solution in described porous support, mix 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, make the mass ratio of described magnesium compound (in the magnesium compound solid containing in described magnesium compound solution) and described porous support reach 1: 0.1-20, preferably 1: 0.5-10, more preferably 1: 1-5.

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

According to the present invention, term " Nonmetallocene title complex " is a kind of single site olefin polymerization catalysts for metallocene catalyst, in structure, do not contain the cyclopentadienyl or derivatives thereofs such as luxuriant ring, fluorenes ring or indenes ring, and when with promotor (such as hereinafter described those) combination, can demonstrate the organometallics (therefore described Nonmetallocene title complex is also sometimes referred to as non-metallocene olefin polymerization title complex) of olefinic polymerization catalysis activity.This compound comprises central metal atom and at least one polydentate ligand of being combined with coordinate bond with described central metal atom (preferably tridentate ligand or more polydentate ligand), and term " Nonmetallocene part " is aforesaid polydentate ligand.

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

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

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

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

At one more specifically in embodiment, described Nonmetallocene title complex is selected from the compound (A-1) with following chemical structural formula to compound (A-4) and compound (B-1) to compound (B-4).

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from periodic table of elements III-th family to XI family atoms metal, preferably IVB family atoms metal, such as enumerating 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 the P coordination atom of respectively doing for oneself;

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group, phosphorus-containing groups or cyano group (CN), such as can enumerate-NR ²³r ²⁴,-N (O) R ²⁵r ²⁶,-PR ²⁸r ²⁹,-P (O) R ³⁰r ³¹,-OR ³⁴,-SR ³⁵,-S (O) R ³⁶,-SeR ³⁸or-Se (O) R ³⁹, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

R ¹to R ⁴, R ⁶to R ³⁶, R ³⁸and R ³⁹be selected from independently of one another hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl (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, and wherein adjacent group is such as R ¹with R ², R ⁶with R ⁷, R ⁷with R ⁸, R ⁸with R ⁹, R ¹³with R ¹⁴, R ¹⁴with R ¹⁵, R ¹⁵with R ¹⁶, R ¹⁸with R ¹⁹, R ¹⁹with R ²⁰, R ²⁰with R ²¹, R ²³with R ²⁴, or R ²⁵with R ²⁶deng combining togather into key or Cheng Huan, be preferably formed aromatic ring, such as unsubstituted phenyl ring or by 1-4 C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl (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 ⁵during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, R ⁵in N, O, S, P and Se can be used as coordination atom and described center IVB family atoms metal carries out coordination.

According to the present invention, in aforementioned all chemical structural formulas, as the case may be, any adjacent two or more groups, such as R ²¹with group Z, or R ¹³with group Y, can combine togather into ring, be preferably formed and comprise the heteroatomic C that comes from described group Z or Y ₆-C ₃₀heteroaromatic, such as pyridine ring etc., wherein said heteroaromatic is optionally selected from C by one or more ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀the substituting group of alkyl and safing function group replaces.

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

In the context of the present invention, described C ₁-C ₃₀alkyl is selected from C ₁-C ₃₀alkyl (preferably C ₁-C ₆alkyl, such as isobutyl-), C ₇-C ₅₀alkaryl (such as tolyl, xylyl, diisobutyl phenyl etc.), C ₇-C ₅₀aralkyl (such as benzyl), C ₃-C ₃₀cyclic alkyl, C ₂-C ₃₀thiazolinyl, C ₂-C ₃₀alkynyl, C ₆-C ₃₀aryl (such as phenyl, naphthyl, anthryl etc.), C ₈-C ₃₀condensed ring radical or C ₄-C ₃₀heterocyclic radical, wherein said heterocyclic radical contains 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom, such as pyridyl, pyrryl, furyl or thienyl etc.

According to the present invention, in the context of the present invention, according to the particular case of the relevant group of its combination, described C ₁-C ₃₀alkyl refers to C sometimes ₁-C ₃₀hydrocarbon two bases (divalent group, or be called C ₁-C ₃₀alkylene) or C ₁-C ₃₀hydrocarbon three bases (trivalent group), this is obvious to those skilled in the art.

In the context of the present invention, the C of described replacement ₁-C ₃₀alkyl refers to the aforementioned C with one or more inert substituents ₁-C ₃₀alkyl.So-called inert substituent, refer to these substituting groups to aforementioned for coordination group (refer to aforementioned group A, D, E, F, Y and Z, or also optionally comprise radicals R ⁵) there is no substantial interference with the coordination process of described central metal atom M; In other words, limit by the chemical structure of polydentate ligand of the present invention, these substituting groups do not have ability or have no chance (such as being subject to the impact of steric hindrance etc.) coordination reaction occurs and form coordinate bond with described central metal atom M.Generally speaking, described inert substituent is such as being selected from aforesaid halogen or C ₁-C ₃₀alkyl (preferably 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, be selected from aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group such as enumerating, contain tin group, C ₁-C ₁₀ester group or nitro (NO ₂) at least one etc.

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

(1) do not disturb the coordination process of described group A, D, E, F, Y or Z and described central metal atom M, and

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

In the context of the present invention, described boron-containing group is selected from BF ₄ ^-, (C ₆f ₅) ₄b ^-or (R ⁴⁰bAr ₃) ^-; Describedly be selected from aluminum alkyls, AlPh containing aluminium base group ₄ ^-, AlF ₄ ^-, AlCl ₄ ^-, AlBr ₄ ^-, AlI ₄ ^-or R ⁴¹alAr ₃ ^-; Be selected from-SiR of described silicon-containing group ⁴²r ⁴³r ⁴⁴or-T-SiR ⁴⁵; Described be selected from-GeR of germanic group ⁴⁶r ⁴⁷r ⁴⁸or-T-GeR ⁴⁹; Described containing be selected from-SnR of tin group ⁵⁰r ⁵¹r ⁵²,-T-SnR ⁵³or-T-Sn (O) R ⁵⁴, wherein Ar represents C ₆-C ₃₀aryl.R ⁴⁰to R ⁵⁴be selected from independently of one another hydrogen, aforesaid C ₁-C ₃₀the C of alkyl, aforesaid replacement ₁-C ₃₀alkyl or aforesaid safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan.Wherein, the definition of group T is the same.

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

Described Nonmetallocene title complex is preferably selected from following compound:

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

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

These Nonmetallocene title complexs can use separately one, or are used in combination multiple with ratio arbitrarily.

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

Described Nonmetallocene title complex or described polydentate ligand can be manufactured according to any method well known by persons skilled in the art.About the particular content of its manufacture method, such as can be referring to WO03/010207 and Chinese patent ZL01126323.7 and ZL02110844.7 etc., the full text that this specification sheets is introduced these documents at this point as a reference.

According to the present invention, in order to measure with easy to operate, described Nonmetallocene title complex uses with the form of solution where necessary.

In the time of the solution of the described Nonmetallocene title complex of preparation, to solvent now used, there is no particular limitation, as long as can dissolve described Nonmetallocene title complex.As described solvent, such as can with described for the solvent phase that dissolves described magnesium compound with solvent etc.Wherein, preferred C _6-12aromatic hydrocarbon and tetrahydrofuran (THF).

These solvents can use separately one, or are used in combination multiple with ratio arbitrarily.

In the time dissolving described Nonmetallocene title complex, can use as required stirring (rotating speed of this stirring is generally 10～500 revs/min).

According to the present invention, easily, described Nonmetallocene title complex is generally 0.01～0.25 grams per milliliter with respect to the ratio of described solvent, preferably 0.05～0.16 grams per milliliter, but be sometimes not limited to this.

According to the present invention, described Nonmetallocene title complex (or its solution) is contacted with described the first mixed serum, can obtain the second mixed serum.

In the time manufacturing described the second mixed serum, to the way of contact of described the first mixed serum and described Nonmetallocene title complex, there is no particular limitation, directly measure the mode of adding described Nonmetallocene title complex such as enumerating in described the first mixed serum, or described Nonmetallocene title complex, according to the aforementioned solution that is mixed with in advance, is then added to the mode etc. of this complex solution to metering in described the first mixed serum.

In addition, in order to manufacture described the second mixed serum, such as can be at normal temperature to the temperature lower than the boiling point of used any solvent, make the contact reacts of described the first mixed serum and described Nonmetallocene title complex carry out 0.1～8h, preferably 0.5～4h, optimum 1～2h (if desired by stirring).

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

Then, by be metered into precipitation agent in described the second mixed serum, solid matter is precipitated out from this mixed serum, obtains load type non-metallocene catalyst of the present invention.

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, porous support Nonmetallocene part or Nonmetallocene title complex etc.) in its solution also and then the unreactiveness liquid that it is separated out with solid form from described solution.

According to the present invention, as described precipitation agent, be poor solvent such as enumerating for solid substance solute to be precipitated (such as described magnesium compound, porous support Nonmetallocene part or Nonmetallocene title complex etc.), and be the solvent of good solvent for the described solvent for dissolving described solid substance solute (such as magnesium compound etc.), such as enumerating C _5-12alkane, C _5-12naphthenic hydrocarbon, halo C _1-10alkane and halo C _5-12naphthenic hydrocarbon.

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

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

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

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

These precipitation agents can use separately one, also can use with the multiple mixing of ratio arbitrarily.

The mode that adds of precipitation agent can add or drip for disposable, preferably disposable adding.In this precipitation process, can utilize to stir to promote the dispersion of precipitation agent, 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 lower than the boiling point of used any solvent and precipitation agent (preferably 20-80 DEG C, more preferably 40-60 DEG C), but be sometimes not limited to this.And, general also preferred temperature (the preferably 20-80 DEG C to the boiling point lower than used any solvent and precipitation agent at normal temperature of this precipitation process, 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, washed and is dried, obtaining thus load type non-metallocene catalyst of the present invention.

Be not particularly limited for described filtration, washing and dry method, can use as required conventional those that use in this area.As required, described washing is generally carried 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 being dried can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or vacuum, and preferably heat drying method, most preferably heat drying method under vacuum under rare gas element desiccating method or vacuum.Described dry temperature range is generally normal temperature to 140 DEG C.Be generally 2-20 hour time of drying, but also can be according to concrete use different for dissolving the solvent situation of described magnesium compound.Such as, in the time adopting tetrahydrofuran (THF) as solvent for dissolving described magnesium compound, drying temperature is generally 80 DEG C of left and right, under vacuum, be dried 2～12 hours, and in the time adopting toluene as solvent for dissolving described magnesium compound, drying temperature is generally 100 DEG C of left and right, under vacuum, is dried 4～24 hours.

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

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

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

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

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

In one embodiment, the invention still further relates to the load type non-metallocene catalyst (sometimes also referred to as carry type non-metallocene calalyst for polymerization of olefine) of being 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 process, wherein using load type non-metallocene catalyst of the present invention as catalyst for olefines polymerizing, make alkene homopolymerization or copolymerization.

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

According to homopolymerization/copolymerization process of the present invention, taking load type non-metallocene catalyst of the present invention as 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 as promotor, make alkene homopolymerization or copolymerization.

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

According to the present invention, to the reactive mode of described alkene homopolymerization/copolymerization process, there is no particular limitation, can adopt well known in the art those, such as enumerating slurry process, substance law and vapor phase process etc., wherein preferred slurries method and vapor phase process.

According to the present invention, as described alkene, such as enumerating C ₂～C ₁₀monoolefine, diolefin, cyclic olefin and other ethylenically unsaturated compounds.

Particularly, as described C ₂～C ₁₂monoolefine, such as enumerating ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene and vinylbenzene etc.; As described cyclic olefin, such as enumerating 1-cyclopentenes and norbornylene etc.; As described diolefin, such as enumerating Isosorbide-5-Nitrae-divinyl, 2,5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc.; And as described other ethylenically unsaturated compounds, such as enumerating vinyl acetate and (methyl) acrylate etc.Wherein, the homopolymerization of optimal ethylene, or the copolymerization of ethene and propylene, 1-butylene or 1-hexene.

According to the present invention, homopolymerization refers to only a kind of polymerization of described alkene, and copolymerization refers to the polymerization between two or more described alkene.

According to the present invention, described promotor is selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt, wherein preferred aikyiaiurnirsoxan beta and aluminum alkyls.

As described aikyiaiurnirsoxan beta, such as enumerating the line style aikyiaiurnirsoxan beta shown in following general formula (I-1): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in following general formula (II-1) :-(Al (R)-O-) _n+2-.

In aforementioned formula, radicals R is same to each other or different to each other (preferably identical), is selected from independently of one another C ₁-C ₈alkyl, preferable methyl, ethyl and isobutyl-, most preferable.N is the arbitrary integer within the scope of 1-50, preferably the arbitrary integer in 10～30 scopes.

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

These aikyiaiurnirsoxan beta can be used separately one, or are used in combination multiple with ratio arbitrarily.

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

Al(R) ₃ (III)

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

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

These aluminum alkylss can use separately one, or are used in combination multiple with ratio arbitrarily.

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

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 independently of one another C ₁-C ₈alkyl, preferable methyl, ethyl and isobutyl-, most preferable.Radicals X is halogen, preferably chlorine.N is 1 or 2.

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

Chloromethyl aluminium triethyl (Al (CH ₃) (CH ₃cH ₂) Cl), chloromethyl propyl group aluminium (Al (CH ₃) (C ₃h ₇) Cl), chloromethyl n-butylaluminum (Al (CH ₃) (C ₄h ₉) Cl), chloromethyl aluminium isobutyl (Al (CH ₃) (i-C ₄h ₉) Cl), a chloroethyl propyl group aluminium (Al (CH ₂cH ₃) (C ₃h ₇) Cl), a chloroethyl n-butylaluminum (AlCH ₂cH ₃) (C ₄h ₉) Cl), chloromethyl aluminium isobutyl (AlCH ₂cH ₃) (i-C ₄h ₉) Cl) etc., wherein 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 aluminium diethyl monochloride most preferably.

These haloalkyl aluminium can use separately one, or are used in combination multiple with ratio arbitrarily.

As described boron fluothane, described boron alkyl and described boron alkyl ammonium salt, can directly use conventional those that use in this area, not special restriction.

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

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

As described polymerization solvent, can use this area carrying out alkene homopolymerization conventional those when poly-, do not limit especially.

As described polymerization solvent, such as enumerating C _4-10alkane (such as butane, pentane, hexane, heptane, octane, nonane or decane etc.), halo C _1-10alkane (such as methylene dichloride), C _6-12naphthenic hydrocarbon (hexanaphthene, suberane, cyclooctane, cyclononane or cyclodecane), C _6-20aromatic hydrocarbon (such as toluene and dimethylbenzene) etc.Wherein, preferably using pentane, hexane, heptane and cyclohexane give is described polymerization solvent, most preferably hexane.

These polymerizations can be used separately one with solvent, or are used in combination multiple with ratio arbitrarily.

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

In addition, according to the present invention, described alkene homopolymerization/copolymerization process can carry out under the condition that has hydrogen to exist, and also can under the condition that there is no hydrogen, carry out.In the situation that existing, the dividing potential drop of hydrogen can be 0.01%～99% of described polymerization pressure, preferably 0.01%～50%, but be sometimes not limited to this.

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

Embodiment

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

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

In load type non-metallocene catalyst, the content of IVB family metal (such as Ti) and Mg element adopts ICP-AES method to measure, and the content of Nonmetallocene part or title complex adopts analyses.

The polymerization activity of catalyzer calculates in accordance with the following methods: after polyreaction finishes, polymerisate in reactor is filtered and is dried, then weigh the quality of this polymerisate, 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, the 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 when mensuration is 150 DEG C.

The viscosity-average molecular weight of polymkeric substance is calculated 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 is perhydronaphthalene with solvent, measuring temperature is 135 DEG C) measure the limiting viscosity of described polymkeric substance, then calculate the viscosity-average molecular weight Mv of described polymkeric substance according to following formula.

Mv＝5.37×10 ⁴×[η] ^1.37

Wherein, η is limiting viscosity.

Embodiment 1

Magnesium compound adopts Magnesium Chloride Anhydrous, solvent for dissolved magnesium compound adopts tetrahydrofuran (THF), and porous support adopts silicon-dioxide, i.e. silica gel, model is the ES757 of Ineos company, before use silica gel is continued to roasting 4h and thermal activation under 600 DEG C, nitrogen atmosphere.Nonmetallocene title complex adopts structure to be compound, precipitation agent adopt hexane.

Take 5g Magnesium Chloride Anhydrous, add after solvent and dissolve completely under normal temperature, obtain magnesium compound solution, then add the silica gel through thermal activation, under normal temperature, stir after 2 hours and form the first mixed serum, then add Nonmetallocene title complex, stir at normal temperatures and within 6 hours, obtain the second mixed serum, then add precipitation agent fully to precipitate, filtration, precipitation agent washing 3 times, each 60ml, under last normal temperature, vacuum-drying obtains load type non-metallocene catalyst.

Wherein proportioning is, magnesium compound and 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; The volume proportion of precipitation agent and solvent is 1: 1.

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

Embodiment 2

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

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

Solvent is changed into toluene, and Nonmetallocene title complex adopts precipitation agent changes hexanaphthene into.

Wherein proportioning is, magnesium compound and 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 solvent volume proportioning are 1: 2.

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

Embodiment 3

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

Porous support adopts aluminium sesquioxide.Aluminium sesquioxide is continued under 700 DEG C, nitrogen atmosphere to roasting 6h.

Magnesium compound is changed into anhydrous magnesium bromide (MgBr ₂), Nonmetallocene title complex adopts solvent is changed into ethylbenzene, and precipitation agent is changed into heptane.

Wherein proportioning is, magnesium compound and 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 solvent volume proportioning are 1: 0.7.

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

Embodiment 4

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

Porous support adopts silica-magnesia mixed oxide (mass ratio 1: 1).Silica-magnesia mixed oxide is continued under 600 DEG C, argon gas atmosphere to roasting 4h.

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

Wherein proportioning is, magnesium compound and 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 solvent volume proportioning are 1: 1.5.

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

Embodiment 5

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

Porous support adopting montmorillonite.Polynite is continued under 400 DEG C, nitrogen atmosphere to roasting 8h.

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

Wherein proportioning is, magnesium compound and 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 solvent volume proportioning are 1: 0.5.

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

Embodiment 6

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%).This polystyrene is continued to dry under 100 DEG C, nitrogen atmosphere 12h.

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

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-6.

Embodiment 7

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

Porous support adopts diatomite.Diatomite is continued under 500 DEG C, nitrogen atmosphere to roasting 8h.

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

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-7.

Embodiment 8

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

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

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

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

Embodiment 9

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

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

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

Embodiment 10

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

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

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

Comparative example A

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

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

Catalyzer is designated as CAT-B.

Embodiment 3 (Application Example)

By catalyzer CAT-1～10 that make in the embodiment of the present invention, CAT-A～B, the homopolymerization of carrying out in accordance with the following methods under the following conditions respectively ethene, 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, 85 DEG C of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 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 finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.

Copolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, 85 DEG C of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, the disposable hexene-1 comonomer 50g that adds, add again hydrogen to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.

Preparing ultrahigh molecular weight polyethylene(UHMWPE) is polymerized to: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.5MPa, 70 DEG C of polymerization temperatures, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, promotor is 100 with catalyst activity metal molar ratio, finally continues to pass into ethene and makes polymerization stagnation pressure constant in 0.5MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 2.

Test-results data by sequence number in table 13 and 4 are known, increase the consumption of promotor, improve promotor and catalyst activity metal molar than time, not remarkable on the impact of polymerization catalyst activity, polymer stacks density and molecular weight distribution.It can be said that brightly, adopt load type non-metallocene catalyst prepared by method provided by the invention only to need fewer promotor consumption just can obtain high olefin polymerizating activity; And the polymkeric substance such as the polyethylene that obtained thus has good polymer morphology and high polymer bulk density.

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

In contrast table 1, the test-results data of sequence number 1 and 3 are known, and after copolymerization, catalyst activity has greatly to be increased, thereby the load type non-metallocene catalyst that explanation adopts method provided by the invention to prepare has comparatively significant comonomer effect.

Test-results data by sequence number 1 in contrast table 1 and comparative example sequence number 14～15 are known, in catalyzer, increase or reduce the add-on of Nonmetallocene title complex, its polymer stacks density decreases, and activity increases thereupon or reduces, but considerable change does not occur molecular weight distribution.Thereby illustrate that Nonmetallocene title complex plays decisive role to catalyst activity and molecular weight distribution.

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

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

Claims

Magnesium compound is dissolved in solvent, obtains the step of magnesium compound solution, wherein said solvent does not comprise alcoholic solvent;

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

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

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

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

6. according to preparation method claimed in claim 1, it is characterized in that, described solvent is selected from C _6-12aromatic hydrocarbon, halo C _6-12one or more in aromatic hydrocarbon, ester and ether.

7. according to preparation method claimed in claim 6, it is characterized in that, described solvent is selected from C _6-12one or more in aromatic hydrocarbon and tetrahydrofuran (THF).

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

In above chemical structural formula,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from periodic table of elements III-th family to XI family 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 the P coordination atom of respectively doing for oneself;

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

R ¹to R ³be selected from independently of one another hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or safing function group, R ²²to R ³³and R ³⁹be selected from independently of one another hydrogen, C ₁-C ₃₀the C of alkyl or replacement ₁-C ₃₀alkyl, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan,

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

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

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

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

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

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

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

Described Ar represents C ₆-C ₃₀aryl, and

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

And described group T ditto defines.

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

In above all chemical structural formulas,

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

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

In above all chemical structural formulas,

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

R ⁵be selected from lone-pair electron on nitrogen, hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R ⁵during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, R ⁵in N, O, S, P and Se can be used as coordination atom and center IVB family atoms metal carries out coordination.

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

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

13. according to preparation method claimed in claim 1, it is characterized in that, 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.

14. according to the preparation method described in claim 13, it is characterized in that, described precipitation agent is selected from one or more in hexane, heptane, decane and hexanaphthene.

15. according to preparation method claimed in claim 1, it is characterized in that, taking the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene title complex as 1: 0.01-1, the ratio of described magnesium compound and described solvent is 1mol: 75～400ml, taking the described magnesium compound of magnesium compound solid and the mass ratio of described porous support as 1: 0.1-20, and the volume ratio of described precipitation agent and described solvent is 1: 0.2～5.

16. 1 kinds of load type non-metallocene catalysts, it is to be manufactured by the preparation method according to described in claim 1-15 any one.

17. 1 kinds of alkene homopolymerization/copolymerization process, it is characterized in that, taking the load type non-metallocene catalyst according to described in claim 16 as 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 as promotor, make alkene homopolymerization or copolymerization.