CN102399318B

CN102399318B - Supported non-metallocene catalyst and preparation method and application thereof

Info

Publication number: CN102399318B
Application number: CN 201010285970
Authority: CN
Inventors: 李传峰; 郭峰; 任鸿平; 阚林; 柏基业; 马忠林; 陈韶辉; 汪开秀; 王亚明; 杨爱武
Original assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Priority date: 2010-09-16
Filing date: 2010-09-16
Publication date: 2013-11-06
Anticipated expiration: 2030-09-16
Also published as: CN102399318A

Abstract

The invention relates to a supported non-metallocene catalyst and a preparation method thereof. The supported non-metallocene catalyst has the characteristics that the preparation process has a large regulation margin, the content of non-metallocene is controllable, and the copolymerization effect is obvious. The invention also relates to the application of the supported non-metallocene catalyst in olefin homopolymerization/copolymerization. And compared with the prior art, the application has the characteristics that activity is high in olefin polymerization catalysis, a polymer has high bulk density and the molecular weight distribution of the polymer can be controlled and adjusted to be narrow.

Description

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

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

Non-metallocene catalyst, claim again luxuriant rear catalyst, come across middle and later periods nineteen nineties, the central atom of Primary Catalysts has comprised nearly all transition metal, reach at some aspect of performance, even surpass metallocene catalyst, become after Ziegler, Ziegler-Natta and metallocene catalyst the 4th generation olefin polymerization catalysis.By the excellent property of the polyolefin products of such catalyzer manufacturing, and low cost of manufacture.The non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and have cis alkyl or halogen metal division center, 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 that forms has the geometric configuration of restriction, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key easily polarizes, and more is conducive to polymerization and the copolymerization of alkene.Therefore, even 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 sticking still, methylaluminoxane consumption are high, and obtain the too low or too high weak point of polymericular weight, only can be used for solution polymerization process or high-pressure polymerization process, seriously limit its industrial applicability.

Patent ZL 01126323.7, ZL 02151294.9 ZL 02110844.7 and WO 03/010207 disclose a kind of alkene homopolymerization/catalyst for copolymerization or catalyst system, has 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 sticking still of polymkeric substance.

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

For patent ZL 01126323.7, ZL 02151294.9 ZL 02110844.7 and the disclosed non-metallocene catalyst of WO03/010207, patent CN 1539855A, CN 1539856A, CN 1789291A, CN 1789292A, CN 1789290A, WO/2006/063501,200510119401.x etc. provide various ways to carry out load obtaining load type non-metallocene catalyst, but these patents all relate on carrier after the Nonmetallocene organic compound that will contain transition metal is carried on processing.

Patent 200610026765.8 discloses a class single active center Z-N olefin polymerization catalysis.This catalyzer, obtains after processing through pretreated carrier (as silica gel), metallic compound (as titanium tetrachloride) and electron donor by adding in magnesium compound (as magnesium chloride)/tetrahydrofuran solution as electron donor with the salicylic alidehyde imine derivative of the salicylic alidehyde imine that contains coordinating group or replacement.

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

Patent 200910180601.4 discloses a kind of preparation method of load type non-metallocene catalyst, it is that magnesium compound and Nonmetallocene title complex are dissolved in solvent, add through dry after the porous support of thermal activation treatment, obtain load type non-metallocene catalyst.Patent 200910180606.7 discloses a kind of preparation method of load type non-metallocene catalyst, it is that magnesium compound and Nonmetallocene title complex are dissolved in solvent, after adding the porous support through thermal activation treatment, after adding precipitation agent, filtration washing is dry again, obtains load type non-metallocene catalyst.What these two kinds of methods were all used is the porous support that thermal activation treatment is crossed, although porous support through thermal activation treatment, dewaters and dehydroxylation, still contains the free hydroxyl of more amount on the surface, follow-up load non-metallocene metal complexes is had a negative impact, limited its active performance.

Chinese patent 200910180602.9 discloses a kind of preparation method of load type non-metallocene catalyst, and it is that magnesium compound and Nonmetallocene title complex are dissolved in solvent, obtains load type non-metallocene catalyst after drying.Patent 200910180605.2 discloses a kind of preparation method of load type non-metallocene catalyst, and it is that magnesium compound and Nonmetallocene title complex are dissolved in solvent, adds the precipitation agent precipitation, obtains load type non-metallocene catalyst after the filtration washing drying.What these two kinds of methods adopted is the magnesium compound carrier, the particle form of catalyzer is difficult to control, and has limited the morphology that polymerization thus obtains.

Patent 200910180603.3,200910180604.8,200910210989.8,200910210986.4,200910210985.X, 200910210990.0 disclosed load type non-metallocene catalyst preparation methods 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 thus obtains.

patent CN200710162667.1, CN200710162676.0 and PCT/CN2008/001739 disclose a kind of magnesium compound load type non-metallocene catalyst and preparation method thereof, it adopts magnesium compound (as magnesium halide, alkyl magnesium, alkoxyl magnesium, alkyl alkoxy magnesium), or magnesium compound passes through chemical treatment, and (treatment agent is aluminum alkyls, aluminum alkoxide) the modification magnesium compound that obtains, or the modification magnesium compound that adopts magnesium compound-tetrahydrofuran (THF)-alcohol to obtain after precipitation is carrier, successively contact by various combination with active metallic compound with the Nonmetallocene part, and the original position load of completing.As single carrier, cause the catalyzer physical strength low due to magnesium compound, easily form fine polymer powder in polymerization process, affected the steady running of polymerization production device.

What Chinese patent 200910180100.6,200910180607.1,200910210988.3,200910210984.5,200910210987.9,200910210991.5 disclosed load type non-metallocene catalyst preparation methods used is the thermal activation treatment porous support of crossing and the magnesium compound solution reaction that contains Nonmetallocene part or Nonmetallocene title complex, last again with the chemical processing agent reaction that contains IVB family metallic compound, obtain load type non-metallocene catalyst.Because IVB family metallic compound is to be distributed on catalyst surface, the polymerization initial activity is higher, and polymerization temperature is controlled difficulty, also is unfavorable for the steady running that polymerization is produced.

CN200710162672.2 discloses a kind of load type non-metallocene catalyst and in-situ preparation method thereof, and it is first to adopt IVB family's metallic compound or Nonmetallocene part to process silica-gel carrier, and then with another mass treatment in the above two.Simple silica gel is lower as the prepared catalyst activity of carrier owing to adopting, and has limited its industrial applications.

Even so, the ubiquitous problem of the load type non-metallocene catalyst that exists in prior art is, the load process is complicated, active ingredient and carrier bonding force a little less than.For the carrier loaded non-metallocene catalyst of porous support list, carrier needs after thermal activation treatment to process with the chemical reagent of its reaction with aluminum alkyls etc. again, needs the strict preparation condition of controlling for the carrier loaded non-metallocene catalyst of magnesium compound list.And the composite carrier load non-metallocene catalyst that forms for porous support and magnesium compound, such as Chinese patent 200410066068.6, and based on load method and a kind of carry type non-metallocene calalyst for polymerization of olefine, its preparation method and the application thereof of the disclosed a kind of high reactivity non-metallocene catalyst of the patent PCT/CN2005/001737 of its application, existence due to alcohol in system, can have a negative impact to load Nonmetallocene title complex performance thereon, limit giving full play to of Nonmetallocene title complex intrinsic performance.

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

Summary of the invention

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

According to the preparation method of this load type non-metallocene catalyst, need not add proton donor and electron donor (such as in this area for this reason and the conventional diether compounds that uses) etc., also need not harsh reaction requirement and reaction conditions.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.

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

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

Make the chemical processing agent and optional porous support reaction through thermal activation treatment, the step that obtains to modify carrier that are selected from IV B family metallic compound;

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

Described modification carrier is mixed with described magnesium compound solution, obtain the step of the first mixed serum;

Add precipitation agent in described the first mixed serum, obtain the step of complex carrier;

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

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

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

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

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

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

5. according to the described preparation method of aforementioned either side, it is characterized in that, described the first solvent is selected from one or more in C6-12 aromatic hydrocarbon, halo C6-12 aromatic hydrocarbon, ester and ether, one or more in preferred C6-12 aromatic hydrocarbon and tetrahydrofuran (THF), tetrahydrofuran (THF) most preferably, and described the second solvent is selected from one or more in C6-12 aromatic hydrocarbon, halo C6-12 aromatic hydrocarbon, halogenated alkane and ether, one or more in preferred C6-12 aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF).

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

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

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

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

A be selected from Sauerstoffatom, sulphur atom, selenium atom, -NR ²³R ²⁴,-N (O) R ²⁵R ²⁶,

-PR ²⁸R ²⁹,-P (O) R ³⁰OR ³¹, sulfuryl, sulfoxide group or-Se (O) R ³⁹, N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

B is selected from nitrogen-atoms, nitrogen-containing group, phosphorus-containing groups or C ₁-C ₃₀Alkyl;

D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C ₁-C ₃₀Alkyl, sulfuryl, sulfoxide group,

-N (O) R ²⁵R ²⁶,

Or-P (O) R ³²(OR ³³), N, O, S, Se and the P coordination atom of respectively doing for oneself wherein;

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

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

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

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

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

R ⁵Be selected from lone-pair electron on nitrogen, hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, contain seleno group or phosphorus-containing groups; Work as R ⁵For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R ⁵In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IV B family atoms metal,

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

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

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

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

Described nitrogen-containing group is selected from

-NR ²³R ²⁴,-T-NR ²³R ²⁴Or-N (O) R ²⁵R ²⁶

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

Described oxy radical be selected from hydroxyl ,-OR ³⁴With-T-OR ³⁴

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

The described seleno group of containing is selected from-SeR ³⁸,-T-SeR ³⁸,-Se (O) R ³⁹Or-T-Se (O) R ³⁹

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

Described R ³⁷Be selected from hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group;

Described C ₁-C ₃₀Alkyl is selected from C ₁-C ₃₀Alkyl, C ₇-C ₅₀Alkaryl, C ₇-C ₅₀Aralkyl, C ₃-C ₃₀Cyclic alkyl, C ₂-C ₃₀Thiazolinyl, C ₂-C ₃₀Alkynyl, C ₆-C ₃₀Aryl, C ₈-C ₃₀Condensed ring radical or C ₄-C ₃₀Heterocyclic radical, wherein said heterocyclic radical contain 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;

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

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

Wherein, described silicon-containing group is selected from-SiR ⁴²R ⁴³R ⁴⁴Or-T-SiR ⁴⁵Described germanic group is selected from-GeR ⁴⁶R ⁴⁷R ⁴⁸Or-T-GeR ⁴⁹Describedly contain tin group and be selected from-SnR ⁵⁰R ⁵¹R ⁵²,-T-SnR ⁵³Or-T-Sn (O) R ⁵⁴Described R ⁴²To R ⁵⁴Be selected from independently of one another hydrogen, aforementioned C ₁-C ₃₀The C of alkyl, aforementioned replacement ₁-C ₃₀Alkyl or aforementioned safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan, and described group T ditto defines.

8. according to the described preparation method of aforementioned either side, it is characterized in that, take the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part as 1: 0.0001-1, preferred 1: 0.0002-0.4, more preferably 1: 0.0008-0.2, further preferred 1: 0.001-0.1, the ratio of described magnesium compound and described the first solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml, take the mass ratio of the described magnesium compound of magnesium compound solid and described porous support as 1: 0.1-20, preferred 1: 0.5-10, more preferably 1: 1-5, the volume ratio of described precipitation agent and described the first solvent is 1: 0.2～5, preferred 1: 0.5～2, more preferably 1: 0.8～1.5, and in the described magnesium compound of Mg element with take the mol ratio of the described chemical processing agent of IV B family metallic element respectively independently of one another as 1: 0.01-1, preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30.

9. according to the described preparation method of aforementioned either side, it is characterized in that, described precipitation agent is selected from alkane, naphthenic hydrocarbon, one or more in halogenated alkane and halo 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, the chloro suberane, the chloro cyclooctane, the chloro cyclononane, the chloro cyclodecane, bromocyclopentane, bromocyclohexane, the bromo suberane, the 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, hexane most preferably.

10. according to the described preparation method of aforementioned either side, it is characterized in that, described IV B family metallic compound is selected from one or more in IV B family metal halide, IV B family metal alkyl compound, IV B family metal alkoxide compound, IV B family's metal alkyl halides and IV B family metal alkoxide halogenide, be preferably selected from one or more in IV B family metal halide, more preferably be selected from TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄And HfBr ₄In one or more, most preferably be selected from TiCl ₄And ZrCl ₄In one or more.

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

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

13. a load type non-metallocene catalyst, it is by making according to the described preparation method of aspect 1-12 any one.

14. alkene homopolymerization/copolymerization process, it is characterized in that, take according to the described load type non-metallocene catalyst in aspect 13 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.

15. an alkene homopolymerization/copolymerization process is characterized in that, comprises the following steps:

The described preparation method of 1-12 any one makes load type non-metallocene catalyst according to the aspect, and

Take 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 variable range of load type non-metallocene catalyst of the present invention is wide, adopt the load type non-metallocene catalyst preparation method technique of method preparation provided by the invention adjustable, olefin polymerizating activity is high, the polymkeric substance such as resulting polyethylene has good polymer morphology and high polymer bulk density thus, and molecular weight distribution is narrower.

When the load type non-metallocene catalyst that employing the present invention obtains and promotor consist of catalyst system, show significant comonomer effect during copolymerization, namely under relatively equal condition, Copolymerization activity is active higher than homopolymerization.

By adopting different load type non-metallocene catalyst preparation technologies, such as regulating Nonmetallocene part consumption, although itself does not have the catalysis in olefine polymerization activity, but itself and chemical processing agent original position generate the Nonmetallocene title complex component with catalytic activity, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst, adapt to thus different olefinic polymerization requirements, thereby and can regulate catalyzer and polymer performance with the preparation process of the add-on of chemical processing agent.

And, find by research, adopt load type non-metallocene catalyst preparation method provided by the invention, due to preparation process do not have alcohol, more can give full play to the intrinsic performance of non-metallocene catalyst, namely resulting molecular weight distribution is narrower thus.

Embodiment

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

The present invention relates to a kind of preparation method of load type non-metallocene catalyst, comprise the following steps: make the chemical processing agent and optional porous support reaction through thermal activation treatment, the step that obtains to modify carrier that are selected from IV B family metallic compound; Magnesium compound is dissolved in the first solvent, obtains the step of magnesium compound solution; Described modification carrier is mixed with described magnesium compound solution, obtain the step of the first mixed serum; Add precipitation agent in described the first mixed serum, obtain the step of complex carrier; Make the chemical processing agent and the reaction of described complex carrier that are selected from described IV B family metallic compound, the step that obtains to modify complex carrier; The Nonmetallocene part is contacted under the existence of the second solvent with described modification complex carrier, obtain the step of the second mixed serum; With described the second mixed serum of convection drying, obtain the step of described load type non-metallocene catalyst.

Below described porous support is specifically described.

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

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

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

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

As described inorganic porous solid, such as 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.) that can enumerate periodic table of elements II A, III A, IV A or IV B family metal, perhaps any infusibility composite oxides of these metals (such as oxidation sial, oxidation magnalium, titanium oxide silicon, titanium oxide magnesium and titanium oxide aluminium etc.), and clay, molecular sieve (such as ZSM-5 and MCM-41), mica, polynite, wilkinite and diatomite etc.As described inorganic porous solid, can also enumerate the oxide compound that is generated by pyrohydrolysis by gaseous metal halogenide or gaseous silicon compound, such as the silica gel that is obtained by the silicon tetrachloride pyrohydrolysis, the aluminum oxide that is perhaps obtained by the aluminum chloride pyrohydrolysis etc.

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

According to the present invention, suitable silicon-dioxide can be by the ordinary method manufacturing, it can be perhaps the commerical prod that can buy arbitrarily, such as Grace 955, the Grace948 that can enumerate Grace company, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245 and Aerosil812, the ES70 of Ineos company, ES70X, ES70Y, ES70W, ES757, EP10X and EP11, and the CS-2133 of Pq Corp. and MS-3040.

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

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

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

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

Below described chemical processing agent is specifically described.

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

As described IV B family metallic compound, such as enumerating IV B family metal halide, IV B family metal alkyl compound, IV B family metal alkoxide compound, IV B family's metal alkyl halides and IV B family metal alkoxide halogenide.

As described IV B family metal halide, described IV B family metal alkyl compound, described IV B family metal alkoxide compound, described IV B family's metal alkyl halides and described IV B family metal alkoxide halogenide, such as the compound that can enumerate following general formula (IV) structure:

M(OR ¹) _mX _nR ² _4-m-n (IV)

Wherein:

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

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

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

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

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

Particularly, as described IV B family metal halide, such as enumerating titanium tetrafluoride (TiF ₄), titanium tetrachloride (TiCl ₄), titanium tetrabromide (TiBr ₄), titanium tetra iodide (TiI ₄);

Zirconium tetrafluoride (ZrF ₄), zirconium tetrachloride (ZrCl ₄), tetrabormated zirconium (ZrBr ₄), zirconium tetraiodide (ZrI ₄);

Tetrafluoride hafnium (HfF ₄), hafnium tetrachloride (HfCl ₄), hafnium (HfBr ₄), tetraiodide hafnium (HfI ₄).

As described IV B family metal alkyl compound, such as enumerating tetramethyl-titanium (Ti (CH ₃) ₄), tetraethyl-titanium (Ti (CH ₃CH ₂) ₄), four isobutyl-titanium (Ti (i-C ₄H ₉) ₄), tetra-n-butyl titanium (Ti (C ₄H ₉) ₄), triethyl methyltitanium (Ti (CH ₃) (CH ₃CH ₂) ₃), diethyl-dimethyl titanium (Ti (CH ₃) ₂(CH ₃CH ₂) ₂), trimethylammonium ethyl titanium (Ti (CH ₃) ₃(CH ₃CH ₂)), triisobutyl methyltitanium (Ti (CH ₃) (i-C ₄H ₉) ₃), diisobutyl dimethyl titanium (Ti (CH ₃) ₂(i-C ₄H ₉) ₂), trimethylammonium isobutyl-titanium (Ti (CH ₃) ₃(i-C ₄H ₉)), triisobutyl ethyl titanium (Ti (CH ₃CH ₂) (i-C ₄H ₉) ₃), diisobutyl diethyl titanium (Ti (CH ₃CH ₂) ₂(i-C ₄H ₉) ₂), triethyl isobutyl-titanium (Ti (CH ₃CH ₂) ₃(i-C ₄H ₉)), three normal-butyl methyltitanium (Ti (CH ₃) (C ₄H ₉) ₃), di-n-butyl dimethyl titanium (Ti (CH ₃) ₂(C ₄H ₉) ₂), trimethylammonium normal-butyl titanium (Ti (CH ₃) ₃(C ₄H ₉)), three normal-butyl methyltitanium (Ti (CH ₃CH ₂) (C ₄H ₉) ₃), di-n-butyl diethyl titanium (Ti (CH ₃CH ₂) ₂(C ₄H ₉) ₂), triethyl normal-butyl titanium (Ti (CH ₃CH ₂) ₃(C ₄H ₉)) etc.;

Tetramethyl-zirconium (Zr (CH ₃) ₄), tetraethyl-zirconium (Zr (CH ₃CH ₂) ₄), four isobutyl-zirconium (Zr (i-C ₄H ₉) ₄), tetra-n-butyl zirconium (Zr (C ₄H ₉) ₄), triethyl methylcyclopentadienyl zirconium (Zr (CH ₃) (CH ₃CH ₂) ₃), diethyl-dimethyl zirconium (Zr (CH ₃) ₂(CH ₃CH ₂) ₂), trimethylammonium ethyl zirconium (Zr (CH ₃) ₃(CH ₃CH ₂)), triisobutyl methylcyclopentadienyl zirconium (Zr (CH ₃) (i-C ₄H ₉) ₃), diisobutyl zirconium dimethyl (Zr (CH ₃) ₂(i-C ₄H ₉) ₂), trimethylammonium isobutyl-zirconium (Zr (CH ₃) ₃(i-C ₄H ₉)), triisobutyl ethyl zirconium (Zr (CH ₃CH ₂) (i-C ₄H ₉) ₃), diisobutyl diethyl zirconium (Zr (CH ₃CH ₂) ₂(i-C ₄H ₉) ₂), triethyl isobutyl-zirconium (Zr (CH ₃CH ₂) ₃(i-C ₄H ₉)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH ₃) (C ₄H ₉) ₃), di-n-butyl zirconium dimethyl (Zr (CH ₃) ₂(C ₄H ₉) ₂), trimethylammonium normal-butyl zirconium (Zr (CH ₃) ₃(C ₄H ₉)), three normal-butyl methylcyclopentadienyl zirconium (Zr (CH ₃CH ₂) (C ₄H ₉) ₃), di-n-butyl diethyl zirconium (Zr (CH ₃CH ₂) ₂(C ₄H ₉) ₂), triethyl normal-butyl zirconium (Zr (CH ₃CH ₂) ₃(C ₄H ₉)) etc.;

Tetramethyl-hafnium (Hf (CH ₃) ₄), tetraethyl-hafnium (Hf (CH ₃CH ₂) ₄), four isobutyl-hafnium (Hf (i-C ₄H ₉) ₄), tetra-n-butyl hafnium (Hf (C ₄H ₉) ₄), triethyl methylcyclopentadienyl hafnium (Hf (CH ₃) (CH ₃CH ₂) ₃), diethyl-dimethyl hafnium (Hf (CH ₃) ₂(CH ₃CH ₂) ₂), trimethylammonium ethyl hafnium (Hf (CH ₃) ₃(CH ₃CH ₂)), triisobutyl methylcyclopentadienyl hafnium (Hf (CH ₃) (i-C ₄H ₉) ₃), diisobutyl dimethyl hafnium (Hf (CH ₃) ₂(i-C ₄H ₉) ₂), trimethylammonium isobutyl-hafnium (Hf (CH ₃) ₃(i-C ₄H ₉)), triisobutyl ethyl hafnium (Hf (CH ₃CH ₂) (i-C ₄H ₉) ₃), diisobutyl diethyl hafnium (Hf (CH ₃CH ₂) ₂(i-C ₄H ₉) ₂), triethyl isobutyl-hafnium (Hf (CH ₃CH ₂) ₃(i-C ₄H ₉)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH ₃) (C ₄H ₉) ₃), di-n-butyl dimethyl hafnium (Hf (CH ₃) ₂(C ₄H ₉) ₂), trimethylammonium normal-butyl hafnium (Hf (CH ₃) ₃(C ₄H ₉)), three normal-butyl methylcyclopentadienyl hafnium (Hf (CH ₃CH ₂) (C ₄H ₉) ₃), di-n-butyl diethyl hafnium (Hf (CH ₃CH ₂) ₂(C ₄H ₉) ₂), triethyl normal-butyl hafnium (Hf (CH ₃CH ₂) ₃(C ₄H ₉)) etc.

As described IV B family metal alkoxide compound, such as enumerating tetramethoxy titanium (Ti (OCH ₃) ₄), purity titanium tetraethoxide (Ti (OCH ₃CH ₂) ₄), four isobutoxy titanium (Ti (i-OC ₄H ₉) ₄), four titanium n-butoxide (Ti (OC ₄H ₉) ₄), triethoxy methoxyl group titanium (Ti (OCH ₃) (OCH ₃CH ₂) ₃), diethoxy dimethoxy titanium (Ti (OCH ₃) ₂(OCH ₃CH ₂) ₂), trimethoxy ethanolato-titanium (Ti (OCH ₃) ₃(OCH ₃CH ₂)), three isobutoxy methoxyl group titanium (Ti (OCH ₃) (i-OC ₄H ₉) ₃), two isobutoxy dimethoxy titanium (Ti (OCH ₃) ₂(i-OC ₄H ₉) ₂), trimethoxy isobutoxy titanium (Ti (OCH ₃) ₃(i-OC ₄H ₉)), three isobutoxy ethanolato-titanium (Ti (OCH ₃CH ₂) (i-OC ₄H ₉) ₃), two isobutoxy diethoxy titanium (Ti (OCH ₃CH ₂) ₂(i-OC ₄H ₉) ₂), triethoxy isobutoxy titanium (Ti (OCH ₃CH ₂) ₃(i-OC ₄H ₉)), three n-butoxy methoxyl group titanium (Ti (OCH ₃) (OC ₄H ₉) ₃), two n-butoxy dimethoxy titanium (Ti (OCH ₃) ₂(OC ₄H ₉) ₂), trimethoxy titanium n-butoxide (Ti (OCH ₃) ₃(OC ₄H ₉)), three n-butoxy methoxyl group titanium (Ti (OCH ₃CH ₂) (OC ₄H ₉) ₃), two n-butoxy diethoxy titanium (Ti (OCH ₃CH ₂) ₂(OC ₄H ₉) ₂), triethoxy titanium n-butoxide (Ti (OCH ₃CH ₂) ₃(OC ₄H ₉)) etc.;

Tetramethoxy zirconium (Zr (OCH ₃) ₄), tetraethoxy zirconium (Zr (OCH ₃CH ₂) ₄), four isobutoxy zirconium (Zr (i-OC ₄H ₉) ₄), four n-butoxy zirconium (Zr (OC ₄H ₉) ₄), triethoxy methoxyl group zirconium (Zr (OCH ₃) (OCH ₃CH ₂) ₃), diethoxy dimethoxy zirconium (Zr (OCH ₃) ₂(OCH ₃CH ₂) ₂), trimethoxy oxyethyl group zirconium (Zr (OCH ₃) ₃(OCH ₃CH ₂)), three isobutoxy methoxyl group zirconium (Zr (OCH ₃) (i-OC ₄H ₉) ₃), two isobutoxy dimethoxy zirconium (Zr (OCH ₃) ₂(i-OC ₄H ₉) ₂), trimethoxy isobutoxy zirconium (Zr (OCH ₃) ₃(i-C ₄H ₉)), three isobutoxy oxyethyl group zirconium (Zr (OCH ₃CH ₂) (i-OC ₄H ₉) ₃), two isobutoxy diethoxy zirconium (Zr (OCH ₃CH ₂) ₂(i-OC ₄H ₉) ₂), triethoxy isobutoxy zirconium (Zr (OCH ₃CH ₂) ₃(i-OC ₄H ₉)), three n-butoxy methoxyl group zirconium (Zr (OCH ₃) (OC ₄H ₉) ₃), two n-butoxy dimethoxy zirconium (Zr (OCH ₃) ₂(OC ₄H ₉) ₂), trimethoxy n-butoxy zirconium (Zr (OCH ₃) ₃(OC ₄H ₉)), three n-butoxy methoxyl group zirconium (Zr (OCH ₃CH ₂) (OC ₄H ₉) ₃), two n-butoxy diethoxy zirconium (Zr (OCH ₃CH ₂) ₂(OC ₄H ₉) ₂), triethoxy n-butoxy zirconium (Zr (OCH ₃CH ₂) ₃(OC ₄H ₉)) etc.;

Tetramethoxy hafnium (Hf (OCH ₃) ₄), tetraethoxy hafnium (Hf (OCH ₃CH ₂) ₄), four isobutoxy hafnium (Hf (i-OC ₄H ₉) ₄), four n-butoxy hafnium (Hf (OC ₄H ₉) ₄), triethoxy methoxyl group hafnium (Hf (OCH ₃) (OCH ₃CH ₂) ₃), diethoxy dimethoxy hafnium (Hf (OCH ₃) ₂(OCH ₃CH ₂) ₂), trimethoxy oxyethyl group hafnium (Hf (OCH ₃) ₃(OCH ₃CH ₂)), three isobutoxy methoxyl group hafnium (Hf (OCH ₃) (i-OC ₄H ₉) ₃), two isobutoxy dimethoxy hafnium (Hf (OCH ₃) ₂(i-OC ₄H ₉) ₂), trimethoxy isobutoxy hafnium (Hf (OCH ₃) ₃(i-OC ₄H ₉)), three isobutoxy oxyethyl group hafnium (Hf (OCH ₃CH ₂) (i-OC ₄H ₉) ₃), two isobutoxy diethoxy hafnium (Hf (OCH ₃CH ₂) ₂(i-OC ₄H ₉) ₂), triethoxy isobutoxy hafnium (Hf (OCH ₃CH ₂) ₃(i-C ₄H ₉)), three n-butoxy methoxyl group hafnium (Hf (OCH ₃) (OC ₄H ₉) ₃), two n-butoxy dimethoxy hafnium (Hf (OCH ₃) ₂(OC ₄H ₉) ₂), trimethoxy n-butoxy hafnium (Hf (OCH ₃) ₃(OC ₄H ₉)), three n-butoxy methoxyl group hafnium (Hf (OCH ₃CH ₂) (OC ₄H ₉) ₃), two n-butoxy diethoxy hafnium (Hf (OCH ₃CH ₂) ₂(OC ₄H ₉) ₂), triethoxy n-butoxy hafnium (Hf (OCH ₃CH ₂) ₃(OC ₄H ₉)) etc.

As described IV B family metal alkyl halides, such as enumerating trimethylammonium titanium chloride (TiCl (CH ₃) ₃), triethyl titanium chloride (TiCl (CH ₃CH ₂) ₃), triisobutyl titanium chloride (TiCl (i-C ₄H ₉) ₃), three normal-butyl chlorination titanium (TiCl (C ₄H ₉) ₃), dimethyl titanium dichloride (TiCl ₂(CH ₃) ₂), diethyl titanium dichloride (TiCl ₂(CH ₃CH ₂) ₂), diisobutyl titanium dichloride (TiCl ₂(i-C ₄H ₉) ₂), three normal-butyl chlorination titanium (TiCl (C ₄H ₉) ₃), methyl titanous chloride (Ti (CH ₃) Cl ₃), ethyl titanous chloride (Ti (CH ₃CH ₂) Cl ₃), isobutyl-titanous chloride (Ti (i-C ₄H ₉) Cl ₃), normal-butyl titanous chloride (Ti (C ₄H ₉) Cl ₃);

Trimethylammonium titanium bromide (TiBr (CH ₃) ₃), triethyl titanium bromide (TiBr (CH ₃CH ₂) ₃), triisobutyl titanium bromide (TiBr (i-C ₄H ₉) ₃), three normal-butyl bromination titanium (TiBr (C ₄H ₉) ₃), dimethyl dibrominated titanium (TiBr ₂(CH ₃) ₂), diethyl dibrominated titanium (TiBr ₂(CH ₃CH ₂) ₂), diisobutyl dibrominated titanium (TiBr ₂(i-C ₄H ₉) ₂), three normal-butyl bromination titanium (TiBr (C ₄H ₉) ₃), methyl titanium tribromide (Ti (CH ₃) Br ₃), ethyl titanium tribromide (Ti (CH ₃CH ₂) Br ₃), isobutyl-titanium tribromide (Ti (i-C ₄H ₉) Br ₃), normal-butyl titanium tribromide (Ti (C ₄H ₉) Br ₃);

Trimethylammonium zirconium chloride (ZrCl (CH ₃) ₃), triethyl zirconium chloride (ZrCl (CH ₃CH ₂) ₃), triisobutyl zirconium chloride (ZrCl (i-C ₄H ₉) ₃), three normal-butyl chlorination zirconium (ZrCl (C ₄H ₉) ₃), dimethyl zirconium dichloride (ZrCl ₂(CH ₃) ₂), diethyl zirconium dichloride (ZrCl ₂(CH ₃CH ₂) ₂), diisobutyl zirconium dichloride (ZrCl ₂(i-C ₄H ₉) ₂), three normal-butyl chlorination zirconium (ZrCl (C ₄H ₉) ₃), methyl tri-chlorination zirconium (Zr (CH ₃) Cl ₃), ethyl tri-chlorination zirconium (Zr (CH ₃CH ₂) Cl ₃), isobutyl-tri-chlorination zirconium (Zr (i-C ₄H ₉) Cl ₃), normal-butyl tri-chlorination zirconium (Zr (C ₄H ₉) Cl ₃);

Trimethylammonium zirconium bromide (ZrBr (CH ₃) ₃), triethyl zirconium bromide (ZrBr (CH ₃CH ₂) ₃), triisobutyl zirconium bromide (ZrBr (i-C ₄H ₉) ₃), three normal-butyl bromination zirconium (ZrBr (C ₄H ₉) ₃), dimethyl dibrominated zirconium (ZrBr ₂(CH ₃) ₂), diethyl dibrominated zirconium (ZrBr ₂(CH ₃CH ₂) ₂), diisobutyl dibrominated zirconium (ZrBr ₂(i-C ₄H ₉) ₂), three normal-butyl bromination zirconium (ZrBr (C ₄H ₉) ₃), methyl tribromide zirconium (Zr (CH ₃) Br ₃), ethyl tribromide zirconium (Zr (CH ₃CH ₂) Br ₃), isobutyl-tribromide zirconium (Zr (i-C ₄H ₉) Br ₃), normal-butyl tribromide zirconium (Zr (C ₄H ₉) Br ₃);

Trimethylammonium hafnium chloride (HfCl (CH ₃) ₃), triethyl hafnium chloride (HfCl (CH ₃CH ₂) ₃), triisobutyl hafnium chloride (HfCl (i-C ₄H ₉) ₃), three normal-butyl chlorination hafnium (HfCl (C ₄H ₉) ₃), dimethyl hafnium dichloride (HfCl ₂(CH ₃) ₂), diethyl hafnium dichloride (HfCl ₂(CH ₃CH ₂) ₂), diisobutyl hafnium dichloride (HfCl ₂(i-C ₄H ₉) ₂), three normal-butyl chlorination hafnium (HfCl (C ₄H ₉) ₃), methyl tri-chlorination hafnium (Hf (CH ₃) Cl ₃), ethyl tri-chlorination hafnium (Hf (CH ₃CH ₂) Cl ₃), isobutyl-tri-chlorination hafnium (Hf (i-C ₄H ₉) Cl ₃), normal-butyl tri-chlorination hafnium (Hf (C ₄H ₉) Cl ₃);

Trimethylammonium bromination hafnium (HfBr (CH ₃) ₃), triethyl bromination hafnium (HfBr (CH ₃CH ₂) ₃), triisobutyl bromination hafnium (HfBr (i-C ₄H ₉) ₃), three normal-butyl bromination hafnium (HfBr (C ₄H ₉) ₃), dimethyl dibrominated hafnium (HfBr ₂(CH ₃) ₂), diethyl dibrominated hafnium (HfBr ₂(CH ₃CH ₂) ₂), diisobutyl dibrominated hafnium (HfBr ₂(i-C ₄H ₉) ₂), three normal-butyl bromination hafnium (HfBr (C ₄H ₉) ₃), methyl tribromide hafnium (Hf (CH ₃) Br ₃), ethyl tribromide hafnium (Hf (CH ₃CH ₂) Br ₃), isobutyl-tribromide hafnium (Hf (i-C ₄H ₉) Br ₃), normal-butyl tribromide hafnium (Hf (C ₄H ₉) Br ₃).

As described IV B family metal alkoxide halogenide, such as enumerating trimethoxy titanium chloride (TiCl (OCH ₃) ₃), triethoxy titanium chloride (TiCl (OCH ₃CH ₂) ₃), three isobutoxy titanium chloride (TiCl (i-OC ₄H ₉) ₃), three n-Butoxyl titanium-chlorides (TiCl (OC ₄H ₉) ₃), dimethoxy titanium dichloride (TiCl ₂(OCH ₃) ₂), diethoxy titanium dichloride (TiCl ₂(OCH ₃CH ₂) ₂), two isobutoxy titanium dichloride (TiCl ₂(i-OC ₄H ₉) ₂), three n-Butoxyl titanium-chlorides (TiCl (OC ₄H ₉) ₃), methoxyl group titanous chloride (Ti (OCH ₃) Cl ₃), oxyethyl group titanous chloride (Ti (OCH ₃CH ₂) Cl ₃), isobutoxy titanous chloride (Ti (i-C ₄H ₉) Cl ₃), n-butoxy titanous chloride (Ti (OC ₄H ₉) Cl ₃);

Trimethoxy titanium bromide (TiBr (OCH ₃) ₃), triethoxy titanium bromide (TiBr (OCH ₃CH ₂) ₃), three isobutoxy titanium bromide (TiBr (i-OC ₄H ₉) ₃), three n-butoxy titanium bromide (TiBr (OC ₄H ₉) ₃), dimethoxy dibrominated titanium (TiBr ₂(OCH ₃) ₂), diethoxy dibrominated titanium (TiBr ₂(OCH ₃CH ₂) ₂), two isobutoxy dibrominated titanium (TiBr ₂(i-OC ₄H ₉) ₂), three n-butoxy titanium bromide (TiBr (OC ₄H ₉) ₃), methoxyl group titanium tribromide (Ti (OCH ₃) Br ₃), oxyethyl group titanium tribromide (Ti (OCH ₃CH ₂) Br ₃), isobutoxy titanium tribromide (Ti (i-C ₄H ₉) Br ₃), n-butoxy titanium tribromide (Ti (OC ₄H ₉) Br ₃);

Trimethoxy zirconium chloride (ZrCl (OCH ₃) ₃), triethoxy zirconium chloride (ZrCl (OCH ₃CH ₂) ₃), three isobutoxy zirconium chloride (ZrCl (i-OC ₄H ₉) ₃), three n-butoxy zirconium chloride (ZrCl (OC ₄H ₉) ₃), dimethoxy zirconium dichloride (ZrCl ₂(OCH ₃) ₂), diethoxy zirconium dichloride (ZrCl ₂(OCH ₃CH ₂) ₂), two isobutoxy zirconium dichloride (ZrCl ₂(i-OC ₄H ₉) ₂), three n-butoxy zirconium chloride (ZrCl (OC ₄H ₉) ₃), methoxyl group tri-chlorination zirconium (Zr (OCH ₃) Cl ₃), oxyethyl group tri-chlorination zirconium (Zr (OCH ₃CH ₂) Cl ₃), isobutoxy tri-chlorination zirconium (Zr (i-C ₄H ₉) Cl ₃), n-butoxy tri-chlorination zirconium (Zr (OC ₄H ₉) Cl ₃);

Trimethoxy zirconium bromide (ZrBr (OCH ₃) ₃), triethoxy zirconium bromide (ZrBr (OCH ₃CH ₂) ₃), three isobutoxy zirconium bromide (ZrBr (i-OC ₄H ₉) ₃), three n-butoxy zirconium bromide (ZrBr (OC ₄H ₉) ₃), dimethoxy dibrominated zirconium (ZrBr ₂(OCH ₃) ₂), diethoxy dibrominated zirconium (ZrBr ₂(OCH ₃CH ₂) ₂), two isobutoxy dibrominated zirconium (ZrBr ₂(i-OC ₄H ₉) ₂), three n-butoxy zirconium bromide (ZrBr (OC ₄H ₉) ₃), methoxyl group tribromide zirconium (Zr (OCH ₃) Br ₃), oxyethyl group tribromide zirconium (Zr (OCH ₃CH ₂) Br ₃), isobutoxy tribromide zirconium (Zr (i-C ₄H ₉) Br ₃), n-butoxy tribromide zirconium (Zr (OC ₄H ₉) Br ₃);

Trimethoxy hafnium chloride (HfCl (OCH ₃) ₃), triethoxy hafnium chloride (HfCl (OCH ₃CH ₂) ₃), three isobutoxy hafnium chloride (HfCl (i-OC ₄H ₉) ₃), three n-butoxy hafnium chloride (HfCl (OC ₄H ₉) ₃), dimethoxy hafnium dichloride (HfCl ₂(OCH ₃) ₂), diethoxy hafnium dichloride (HfCl ₂(OCH ₃CH ₂) ₂), two isobutoxy hafnium dichloride (HfCl ₂(i-OC ₄H ₉) ₂), three n-butoxy hafnium chloride (HfCl (OC ₄H ₉) ₃), methoxyl group tri-chlorination hafnium (Hf (OCH ₃) Cl ₃), oxyethyl group tri-chlorination hafnium (Hf (OCH ₃CH ₂) Cl ₃), isobutoxy tri-chlorination hafnium (Hf (i-C ₄H ₉) Cl ₃), n-butoxy tri-chlorination hafnium (Hf (OC ₄H ₉) Cl ₃);

Trimethoxy bromination hafnium (HfBr (OCH ₃) ₃), triethoxy bromination hafnium (HfBr (OCH ₃CH ₂) ₃), three isobutoxy bromination hafnium (HfBr (i-OC ₄H ₉) ₃), three n-butoxy bromination hafnium (HfBr (OC ₄H ₉) ₃), dimethoxy dibrominated hafnium (HfBr ₂(OCH ₃) ₂), diethoxy dibrominated hafnium (HfBr ₂(OCH ₃CH ₂) ₂), two isobutoxy dibrominated hafnium (HfBr ₂(i-OC ₄H ₉) ₂), three n-butoxy bromination hafnium (HfBr (OC ₄H ₉) ₃), methoxyl group tribromide hafnium (Hf (OCH ₃) Br ₃), oxyethyl group tribromide hafnium (Hf (OCH ₃CH ₂) Br ₃), isobutoxy tribromide hafnium (Hf (i-C ₄H ₉) Br ₃), n-butoxy tribromide hafnium (Hf (OC ₄H ₉) Br ₃).

As described IV B family metallic compound, preferred described IV B family metal halide, more preferably TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄And HfBr ₄, TiCl most preferably ₄And ZrCl ₄

These IV B family metallic compound can be used alone, and perhaps is used in combination multiple with ratio arbitrarily.

According to the present invention, make the chemical processing agent and the described optional porous support reaction through thermal activation treatment that are selected from described IV B family metallic compound, obtain to modify carrier (hereinafter referred to as chemical treatment reaction I); Perhaps, make the chemical processing agent that is selected from described IV B family metallic compound and complex carrier reaction as described below, obtain to modify complex carrier (hereinafter referred to as chemical treatment reaction II).

According to the present invention, in described chemical treatment reaction I and described chemical treatment reaction II, the described chemical processing agent that uses separately can be the same or different.

As the mode of carrying out described chemical treatment reaction I or chemical treatment reaction II (unless otherwise indicated, following content will be applicable to described chemical treatment reaction I and II simultaneously), such as enumerating following content.

When described chemical processing agent is liquid state at normal temperatures, can use described chemical processing agent by the mode that directly drips the described chemical processing agent of predetermined amount in the reaction object that remains to utilize this chemical processing agent to process (such as described optional through the porous support of thermal activation treatment or complex carrier as described below, as follows).

When described chemical processing agent when being solid-state at normal temperatures, for measure with easy to operate for the purpose of, preferably use described chemical processing agent with the form of solution.Certainly, when described chemical processing agent is liquid state at normal temperatures, sometimes also can use described chemical processing agent with the form of solution as required, not special the restriction.

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

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

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

There is no particular limitation to the concentration of described chemical processing agent in its solution, can suitably select as required, as long as it can realize implementing described chemical treatment with the described chemical processing agent of predetermined amount.As previously mentioned, if chemical processing agent is liquid, can directly carry out described processing with chemical processing agent, but use after also it can being modulated into the chemical treatment agent solution.That the volumetric molar concentration of described chemical processing agent in its solution generally is set as 0.01～1.0mol/L, but is not limited to this easily.

As carrying out described chemically treated method, such as enumerating, in the situation that adopt solid chemical processing agent (such as zirconium tetrachloride), at first the solution for preparing described chemical processing agent, then to pending reaction object (such as described optional through thermal activation treatment porous support or complex carrier as described below) in add the described chemical processing agent of (the preferred dropping) predetermined amount; in the situation that adopt liquid chemical treatment agent (such as titanium tetrachloride), can be directly (but also can after being prepared into solution) the described chemical processing agent of predetermined amount is added in (the preferred dropping) pending reaction object (such as described optional through the porous support of thermal activation treatment or complex carrier as described below), and chemical treatment reaction (in case of necessity by stirring) was carried out 0.5～24 hour, preferred 1～8 hour, more preferably 2～6 hours, then filter, washing and dry getting final product.

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

So far, by aforesaid chemical treatment reaction I, obtained the modification carrier.

Below described magnesium compound is specifically described.

According to the present invention, term " magnesium compound " uses the common concept in this area, refers to as the conventional organic or inorganic solid water-free magnesium-containing compound that uses of the carrier of supported olefin polymerization catalyst.

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

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

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

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

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

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

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

These magnesium compounds can be used alone, and also can multiple mixing use, not special restriction.

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

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

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

Particularly, described magnesium compound (solid) is dissolved in suitable solvent (namely being used for dissolving the solvent of described magnesium compound, perhaps the first solvent), thereby obtains described magnesium compound solution.

As described the first solvent, such as enumerating C _6-12Aromatic hydrocarbon, halo C _6-12Aromatic hydrocarbon, ester and ether equal solvent.Specifically such as enumerating toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, ethyl acetate and tetrahydrofuran (THF) etc.Wherein, preferred C _6-12Aromatic hydrocarbon and tetrahydrofuran (THF), most preferably tetrahydrofuran (THF).

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

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

In order to prepare described magnesium compound solution, described magnesium compound metering is added to dissolve in described the first solvent to getting final product.When the described magnesium compound solution of preparation, ratio in the described magnesium compound (solid) of magnesium elements and the described solvent (the first solvent) that is used for dissolving described magnesium compound is generally 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml.

There is no particular limitation to the preparation time (being the dissolution time of described magnesium compound etc.) of described magnesium compound solution, but be generally 0.5～24h, preferred 4～24h.In this preparation process, can utilize and stir the dissolving promote described magnesium compound etc.This stirring can be adopted any form, such as stirring rake (rotating speed is generally 10～1000 rev/mins) etc.As required, sometimes can promote dissolving by suitable heating (but top temperature must lower than the boiling point of described solvent).

Then, mix with described magnesium compound solution by making described modification carrier, obtain thus the first mixed serum.

According to the present invention, the mixing process of described modification carrier and described magnesium compound solution can adopt usual method to carry out, and there is no particular limitation.Such as enumerating, at normal temperature to the preparation temperature of described magnesium compound solution, be metered into described modification carrier in described magnesium compound solution, perhaps be metered into described magnesium compound solution in described modification carrier, mix 0.1～8h, preferred 0.5～4h, optimum 1～2h (in case of necessity by stirring) gets final product.

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

Then, by be metered into precipitation agent in described the first mixed serum, solid matter is precipitated out from this mixed serum, obtains thus complex carrier.

Below described precipitation agent is specifically described.

According to the present invention, term " precipitation agent " uses the common concept in this area, refers to can reduce the solubleness of solute (such as described magnesium compound) 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 described magnesium compound, and be the solvent of good solvent for the described solvent that is used for dissolving described magnesium compound, such as enumerating alkane, naphthenic hydrocarbon, halogenated alkane and halo naphthenic hydrocarbon.

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

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

As described halogenated alkane, 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 naphthenic 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 be used alone, and also can use with the multiple mixing of ratio arbitrarily.

The mode that adds of precipitation agent can add or drip for disposable, preferred 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 be adopted any form, such as stirring rake (rotating speed is generally 10～1000 rev/mins) etc.

Also there is no particular limitation to the temperature of described precipitation agent, but general preferred normal temperature.And this precipitation process is generally also preferably carried out at normal temperatures.

Fully after the precipitation, the solid product that obtains is filtered, washs and drying, can obtain described complex carrier.For described filtration, washing and the dry not special restriction of method, can use as required conventional those that use in this area.As required, described washing is generally carried out 1～6 time, preferred 2～3 times.Wherein, washer solvent preferably uses the solvent identical with precipitation agent, but also can be different.

Described drying can adopt ordinary method to carry out, such as heat drying method under rare gas element desiccating method, boulton process or vacuum, and heat drying method, most preferably heat drying method under vacuum under preferred rare gas element desiccating method or vacuum.

The temperature range of described drying is generally normal temperature to 100 ℃, and time of drying with drying until quality of material no longer reduces is limited.Such as, when adopting the tetrahydrofuran (THF) conduct to be used for dissolving the solvent of described magnesium compound, drying temperature is generally 80 ℃ of left and right, got final product in dry 2～12 hours under vacuum, and when adopting the toluene conduct to be used for dissolving the solvent of described magnesium compound, drying temperature is generally 100 ℃ of left and right, gets final product in dry 4～24 hours under vacuum.

Then, by aforesaid chemical treatment reaction II, make described chemical processing agent and described complex carrier carry out chemical reaction, obtain thus described modification complex carrier.

In described chemical treatment reaction II, owing to containing described magnesium compound in described complex carrier, so obviously, just can not select and have the solvent of stripping capacity to dissolve described chemical processing agent to described magnesium compound this moment, to avoid the inappropriate stripping of these materials in treating processes.

According to the present invention, term " Nonmetallocene title complex " refers to a kind of organometallics (therefore described Nonmetallocene title complex is also sometimes referred to as the non-metallocene olefin polymerization title complex) that can demonstrate the olefinic polymerization catalysis activity when making up with aikyiaiurnirsoxan beta, this compound comprises the polydentate ligand (preferably tridentate ligand or more polydentate ligand) that central metal atom and at least one and described central metal atom are combined with coordinate bond, and term " Nonmetallocene part " is aforesaid polydentate ligand.

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

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

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

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

In above all chemical structural formulas,

Q is 0 or 1;

D is O or 1;

A be selected from Sauerstoffatom, sulphur atom, selenium atom,

-NR ²³R ²⁴,-N (O) R ²⁵R ²⁶,

-N (O) R ²⁵R ²⁶,

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

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

R ¹To R ⁴, R ⁶To R ³⁶, R ³⁸And R ³⁹Be selected from independently of one another hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl (preferred halo alkyl wherein, such as-CH ₂Cl and-CH ₂CH ₂Cl) or the safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group is such as R ¹With R ², R ⁶With R ⁷, R ⁷With R ⁸, R ⁸With R ⁹, R ¹³With R ¹⁴, R ¹⁴With R ¹⁵, R ¹⁵With R ¹⁶, R ¹⁸With R ¹⁹, R ¹⁹With R ²⁰, R ²⁰With R ²¹, R ²³With R ²⁴, perhaps R ²⁵With R ²⁶Deng combining togather into key or Cheng Huan, be preferably formed aromatic ring, such as unsubstituted phenyl ring or by 1-4 C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl (preferred halo alkyl wherein, such as-CH ₂Cl and-CH ₂CH ₂Cl) or the phenyl ring that replaces of safing function group; 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, contain seleno group or phosphorus-containing groups; Work as R ⁵For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R ⁵In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IV B family atoms metal.

According to the present invention, in aforementioned all chemical structural formulas, as the case may be, any adjacent two or more groups are such as R ²¹With group Z, perhaps R ¹³With group Y, can combine togather into ring, be preferably formed and comprise the heteroatomic C that comes from described group Z or Y ₆-C ₃₀Heteroaromatic, such as pyridine ring etc., wherein said heteroaromatic is optional is 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 be selected from hydroxyl ,-OR ³⁴With-T-OR ³⁴

Described group T is selected from C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group; With

Described R ³⁷Be selected from hydrogen, C ₁-C ₃₀The C of alkyl, replacement ₁-C ₃₀Alkyl or safing function group.

In the context of the present invention, described C ₁-C ₃₀Alkyl is selected from C ₁-C ₃₀Alkyl (preferred C ₁-C ₆Alkyl is such as isobutyl-), C ₇-C ₅₀Alkaryl (such as tolyl, xylyl, diisobutyl phenyl etc.), C ₇-C ₅₀Aralkyl (such as benzyl), C ₃-C ₃₀Cyclic alkyl, C ₂-C ₃₀Thiazolinyl, C ₂-C ₃₀Alkynyl, C ₆-C ₃₀Aryl (such as phenyl, naphthyl, anthryl etc.), C ₈-C ₃₀Condensed ring radical or C ₄-C ₃₀Heterocyclic radical, wherein said heterocyclic radical contain 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom, such as pyridyl, pyrryl, furyl or thienyl etc.

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

In the context of the present invention, the C of described replacement ₁-C ₃₀Alkyl refers to the aforementioned C with one or more inert substituents ₁-C ₃₀Alkyl.So-called inert substituent refers to these substituting groups aforementioned coordination (is referred to aforementioned group A, D, E, F, Y and Z, perhaps also chooses wantonly and comprise R with group ⁵) there is no substantial interference with the coordination process of central metal atom (aforementioned IV B family atoms metal); In other words, limit by the chemical structure of part of the present invention, these substituting groups do not have ability or have no chance (such as the impact that is subject to steric hindrance etc.) forms coordinate bond with described IV B family's atoms metal generation coordination reaction.Generally speaking, described inert substituent refers to aforementioned halogen or C ₁-C ₃₀Alkyl (preferred C ₁-C ₆Alkyl is such as isobutyl-).

In the context of the present invention, described safing function group does not comprise aforesaid C ₁-C ₃₀The C of alkyl and aforesaid replacement ₁-C ₃₀Alkyl.As described safing function group, such as enumerating aforementioned halogen, aforementioned oxy radical, aforementioned nitrogen-containing group, silicon-containing group, germanic group, aforementioned sulfur-containing group, containing tin group, C ₁-C ₁₀Ester group and nitro (NO ₂) etc.

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

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

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

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

As described Nonmetallocene part, such as enumerating following compound:

Described Nonmetallocene part is preferably selected from following compound:

Described Nonmetallocene part further is preferably selected from following compound:

Described Nonmetallocene part more preferably is selected from following compound:

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

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

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

Then, make described modification complex carrier contact (contact reacts) with described Nonmetallocene part under the existence of the second solvent, can obtain described the second mixed serum.

By described contact reacts, make the described IV B family's metallic compound and the described Nonmetallocene part generation coordination reaction that contain in described modification complex carrier, on complex carrier, original position generates Nonmetallocene title complex (original position load reaction) thereby modify at this.

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

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

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

According to the present invention, when making described the second mixed serum, there is no particular limitation to described the second solvent (below be sometimes referred to as dissolving Nonmetallocene part solvent), needs only it and can dissolve described Nonmetallocene part but the described magnesium compound of not stripping.As described the second solvent, such as enumerating one or more in C6-12 aromatic hydrocarbon, halo C6-12 aromatic hydrocarbon, halogenated alkane and ether.Specifically such as enumerating toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene, methylene dichloride and tetrahydrofuran (THF) etc.Wherein, preferred C6-12 aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).

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

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

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

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

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

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

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

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

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

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

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

As described aluminum alkyls, such as enumerating the compound shown in 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-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), three hexyl aluminium (Al (C ₆H ₁₃) ₃), three isohexyl aluminium (Al (i-C ₆H ₁₃) ₃), diethylmethyl aluminium (Al (CH ₃) (CH ₃CH ₂) ₂) and dimethyl ethyl aluminium (Al (CH ₃CH ₂) (CH ₃) ₂) etc., wherein preferred trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.

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

According to the present invention, as the described chemical processing agent that helps, can only adopt described aikyiaiurnirsoxan beta, also can only adopt described aluminum alkyls, but also can adopt any mixture of described aikyiaiurnirsoxan beta and described aluminum alkyls.And there is no particular limitation to the ratio of each component in this mixture, can select arbitrarily as required.

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

Equally, in described pre-treatment step, owing to containing described magnesium compound in described complex carrier, so obviously just can not select and have the solvent of stripping capacity to dissolve the described chemical processing agent that helps to described magnesium compound this moment, to avoid the inappropriate stripping at magnesium compound described in treating processes.

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

as carrying out described pretreated method, such as enumerating, at first prepare the described solution that helps chemical processing agent, then at the temperature of-30～60 ℃ (preferred-20～30 ℃), to intending being metered into (the preferred dropping) described chemical treatment agent solution (the described chemical processing agent that helps that contains predetermined amount) that helps with described helping in the pretreated described complex carrier of chemical processing agent, perhaps add described complex carrier to the described chemical treatment agent solution amount of falling into a trap that helps, form thus reaction mixture, make its reaction 1～8h, preferred 2～6h, most preferably 3～4h (in case of necessity by stirring) gets final product.Then, the pre-treatment product process that obtains is filtered, washed (1～6 time, preferred 1～3 time) and optionally drying, and separate from this reaction mixture, perhaps, also can be without this separation and be directly used in follow-up reactions steps with the form of mixed solution.At this moment, owing to having contained a certain amount of solvent in described mixed solution, so the solvent load that relates in can the described subsequent reactions step of corresponding minimizing.

Through described pre-treatment step, obtain through pretreated complex carrier thus.Then, then react II according to carrying out described chemical treatment with aforementioned identical mode with described chemical processing agent, just described complex carrier is replaced with the pretreated complex carrier of described process and get final product.Namely, by reacting with aforementioned same chemical treatment, make the chemical processing agent and the pretreated complex carrier of described process that are selected from described IV B family metallic compound react to make the modification complex carrier, and further according to making load type non-metallocene catalyst of the present invention with same before mode.

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

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

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

According to the present invention, in described chemical treatment reaction I and described chemical treatment reaction II, the consumption of described chemical processing agent can be the same or different, select independently of one another, thereby make in the described magnesium compound (solid) of Mg element and mol ratio in the described chemical processing agent of IV B family's metal (such as Ti) element and reach independently of one another 1 in each chemical treatment reaction: 0.01-1, preferred 1: 0.01-0.50, more preferably 1: 0.10-0.30.

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

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

Known to those skilled in the artly be that aforementioned all method steps all preferably carries out under the condition of anhydrous anaerobic basically.Here the said anhydrous anaerobic basically content that refers to water and oxygen in system continues less than 10ppm.And load type non-metallocene catalyst of the present invention needs usually afterwards in confined conditions in preparation that pressure-fired saves backup.

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

In a further embodiment, the present invention relates to a kind of alkene homopolymerization/copolymerization process, wherein with load type non-metallocene catalyst of the present invention as catalyst for olefines polymerizing, make alkene homopolymerization or copolymerization.

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

According to homopolymerization/copolymerization process of the present invention, take load type non-metallocene catalyst of the present invention as Primary Catalysts, to be selected from 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, perhaps first add promotor, and then add Primary Catalysts, or both add after first contacting mixing together, perhaps add simultaneously respectively.Primary Catalysts and promotor are added respectively fashionablely both can add successively in same reinforced pipeline, also can add successively in the reinforced pipeline of multichannel, and both add simultaneously respectively and fashionablely should select the multichannel pipeline that feeds in raw material.For the continous way polyreaction, the reinforced pipeline of preferred multichannel adds simultaneously continuously, and for the intermittence type polymerization reaction, adds together in same reinforced pipeline after preferably both first mix, perhaps first add promotor in same reinforced pipeline, and then add Primary Catalysts.

According to the present invention, there is no particular limitation to the reactive mode of described alkene homopolymerization/copolymerization process, can adopt well known in the art those, such as enumerating slurry process, emulsion method, solution method, 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 ₁₀Monoolefine is such as enumerating ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene and vinylbenzene etc.; As described cyclic olefin, such as enumerating 1-cyclopentenes and norbornylene etc.; As described diolefin, such as enumerating Isosorbide-5-Nitrae-divinyl, 2,5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc.; And as described other ethylenically unsaturated compounds, such as enumerating vinyl acetate and (methyl) acrylate etc.Wherein, the homopolymerization of optimal ethylene, the perhaps copolymerization of ethene and propylene, 1-butylene or 1-hexene.

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

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.

As described aluminum alkyls, such as enumerating the compound shown in following general formula (III-1):

Al(R) ₃ (III-1)

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

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

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

According to the present invention, the difference according to the reactive mode of described alkene homopolymerization/copolymerization process needs to use the polymerization solvent sometimes.

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

As described polymerization solvent, such as enumerating C _4-10Alkane (such as butane, pentane, hexane, heptane, octane, nonane or decane etc.), halo C _1-10Alkane (such as methylene dichloride), aromatic hydrocarbon solvent (such as toluene and dimethylbenzene) etc.Wherein, preferably use hexane as described polymerization solvent.

These polymerizations can be used alone with solvent, perhaps are used in combination multiple with ratio arbitrarily.

According to the present invention, the polymerization pressure of described alkene homopolymerization/copolymerization process is generally 0.1～10MPa, preferred 0.1～4MPa, and more preferably 1～3MPa, but sometimes be not limited to this.According to the present invention, polymeric reaction temperature is generally-40 ℃～200 ℃, and preferred 10 ℃～100 ℃, more preferably 40 ℃～90 ℃, but sometimes be not limited to this.

In addition, according to the present invention, described alkene homopolymerization/copolymerization process can carry out under the condition that has hydrogen to exist, and also can carry out under the condition of hydrogen not having.In the situation that exist, the dividing potential drop of hydrogen can be 0.01%～99% of described polymerization pressure, and is preferred 0.01%～50%, but sometimes is not limited to this.

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

Embodiment

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

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

In load type non-metallocene catalyst, the content of IV B family's metal (such as Ti) and Mg element adopts the ICP-AES method to measure, and the content of Nonmetallocene part adopts analyses.

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

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

Embodiment 1

Porous support adopts silicon-dioxide, i.e. silica gel, and model is the ES757 of Ineos company, at first silica gel is continued roasting 4h and thermal activation under 600 ℃, nitrogen atmosphere.

Chemical processing agent adopts titanium tetrachloride (TiCl ₄).Take the silica gel after the 5g thermal activation, add the 60ml hexane, add titanium tetrachloride under the stirring at normal temperature condition, after reaction 2h under 60 ℃, filter, hexane washing 3 times, each 60ml, last vacuum is drained and is obtained modifying carrier.

Magnesium compound adopts Magnesium Chloride Anhydrous, and the solvent of dissolved magnesium compound adopts tetrahydrofuran (THF), and chemical processing agent adopts titanium tetrachloride.The Nonmetallocene part adopts structure to be

Compound.

Take Magnesium Chloride Anhydrous, add ℃ dissolving fully of the first solvents tetrahydrofurane post-heating to 60, then add the modification carrier, stir after 2 hours, obtain the first mixed serum, then add the precipitation agent hexane to make it precipitation, filter, wash 2 times, each dosage of scour is with add-on is identical before, vacuumize drying under homogeneous heating to 60 ℃, obtain complex carrier.

Then add the 60ml hexane in described complex carrier, with dripping titanium tetrachloride in 30 minutes, 60 ℃ of lower stirring reactions 4 hours, filter under agitation condition, hexane washing 2 times, each hexane consumption 60ml, under normal temperature, vacuum-drying obtains modifying complex carrier.

Take described Nonmetallocene part, be dissolved in fully in the second solvents tetrahydrofurane solvent, disposablely add described modification complex carrier, stirred 4 hours under normal temperature, obtain the second mixed serum, under last normal temperature, vacuum-drying obtains load type non-metallocene catalyst.

Wherein proportioning is, take the mol ratio of the described magnesium compound of Mg element and Nonmetallocene part as 1: 0.05, be 1: 0.20 twice with the mol ratio of chemical processing agent, with the ratio of the first solvent be 1mol: 240ml, take the mass ratio of the described magnesium compound of magnesium compound solid and porous support as 1: 2, the volume ratio of precipitation agent and described the first solvent is 1: 1.

Described load type non-metallocene catalyst is designated as CAT-1.

Embodiment 2

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

Before chemical processing agent is processed the complex carrier reaction, first select and help chemical processing agent methylaluminoxane (MAO, 10wt% toluene solution) to process complex carrier.

Wherein, take the magnesium compound of Mg element with help the mol ratio of chemical processing agent methylaluminoxane as 1: 0.3.

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

Embodiment 3

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

Before chemical processing agent is processed the complex carrier reaction, first select triethyl aluminum (TEAL, 15wt% hexane solution) to process complex carrier.

Wherein, take the magnesium compound of Mg element with help the mol ratio of chemical processing agent triethyl aluminum as 1: 0.5.

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

Embodiment 4

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

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

The Nonmetallocene part adopts

The first and second solvents are changed into toluene, and precipitation agent is changed into hexanaphthene, and chemical processing agent is changed into zirconium tetrachloride (ZrCl ₄).

Wherein proportioning is, take the mol ratio of the described magnesium compound of Mg element and Nonmetallocene part as 1: 0.15, be 1: 0.30 twice with the mol ratio of chemical processing agent, with the ratio of the first solvent be 1mol: 150ml, take the mass ratio of the described magnesium compound of magnesium compound solid and porous support as 1: 1, the volume ratio of precipitation agent and described the first solvent is 1: 1.5.

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

Embodiment 5

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

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

Magnesium compound is changed into anhydrous magnesium bromide (MgBr ₂), the Nonmetallocene part adopts

The first and second solvents are changed into ethylbenzene, and precipitation agent is changed into suberane, and chemical processing agent is changed into titanium tetrabromide (TiBr ₄).

Wherein proportioning is, take the mol ratio of the described magnesium compound of Mg element and Nonmetallocene part as 1: 0.2, be 1: 0.50 twice with the mol ratio of chemical processing agent, with the ratio of the first solvent be 1mol: 300ml, take the mass ratio of the described magnesium compound of magnesium compound solid and porous support as 1: 5, the volume ratio of precipitation agent and described the first solvent is 1: 0.6.

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

Embodiment 6

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

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

Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC ₂H ₅)), the Nonmetallocene part adopts

The first and second solvents are changed into dimethylbenzene, and precipitation agent is changed into decane, and chemical processing agent adopts tetraethyl-titanium (Ti (CH ₃CH ₂) ₄).

Wherein proportioning is, take the mol ratio of the described magnesium compound of Mg element and Nonmetallocene part as 1: 0.01, be 1: 0.05 twice with the mol ratio of chemical processing agent, with the ratio of the first solvent be 1mol: 200ml, take the mass ratio of the described magnesium compound of magnesium compound solid and porous support as 1: 0.5, the volume ratio of precipitation agent and described the first solvent is 1: 0.5.

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

Embodiment 7

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

The porous support adopting montmorillonite.Polynite is continued roasting 8h under 400 ℃, nitrogen atmosphere.

Magnesium compound is changed into butoxy magnesium bromide (MgBr (OC ₄H ₉)), the Nonmetallocene part adopts

The first and second solvents are changed into diethylbenzene, and complex carrier is processed with chemical processing agent and adopted tetra-n-butyl titanium (Ti (C ₄H ₉) ₄).

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

Embodiment 8

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

Porous support adopts the polystyrene of partial cross-linked (degree of crosslinking is 30%).This polystyrene is continued oven dry 12h under 85 ℃, nitrogen atmosphere.

Magnesium compound is changed into methylmagnesium-chloride (Mg (CH ₃) Cl), the Nonmetallocene part adopts

The first and second solvents are changed into chlorotoluene, and chemical processing agent adopts tetraethyl-zirconium (Zr (CH ₃CH ₂) ₄).

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

Embodiment 9

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

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

Magnesium compound is changed into magnesium ethide (Mg (C ₂H ₅) ₂), the Nonmetallocene part adopts

Chemical processing agent adopts isobutyl-titanous chloride (Ti (i-C ₄H ₉) Cl ₃).Load type non-metallocene catalyst is designated as CAT-9.

Reference example 1-A

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

Do not add the Nonmetallocene part.

Catalyzer is designated as CAT-1-A.

Reference example 1-B

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

Take the mol ratio of the described magnesium compound of Mg element and Nonmetallocene part as 1: 1;

Catalyzer is designated as CAT-1-B.

Reference example 1-C

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

Take the mol ratio of the described magnesium compound of Mg element and Nonmetallocene part as 1: 0.25;

Catalyzer is designated as CAT-1-C.

Reference example 1-D

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

Complex carrier is processed without the titanium tetrachloride chemical processing agent.

Catalyzer is designated as CAT-1-D.

Reference example 1-E

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

Add a small amount of ethanol in the solvents tetrahydrofurane of dissolved magnesium compound, make mol ratio take the described magnesium compound of Mg element and ethanol as 1: 2.

Catalyzer is designated as CAT-1-E.

Embodiment 10 (Application Example)

The load type non-metallocene catalyst CAT-1 that makes in the embodiment of the present invention～9, CAT-1-A～E are carried out respectively homopolymerization and the copolymerization of ethene under the following conditions in accordance with the following methods.

Homopolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.At first 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture (promotor with take IVB family metal load type non-metallocene catalyst mol ratio as 100: 1), add again hydrogen to 0.2MPa, continue at last to pass into ethene and make the polymerization stagnation pressure constant in 0.8MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry rear weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.

Copolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.At first 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, the disposable 1-hexene co-monomer 50g that adds, add again hydrogen to 0.2MPa, continue at last to pass into ethene and make the polymerization stagnation pressure constant in 0.8MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry rear weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.

Table 1. load type non-metallocene catalyst is used for olefinic polyreaction effect table look-up

By test result data in table 1 as can be known, adopt the load type non-metallocene catalyst of method preparation provided by the invention to have high olefin polymerizating activity, the polymkeric substance such as resulting polyethylene has good polymer morphology and high polymer bulk density thus, and molecular weight distribution is narrower, those skilled in the art know, the molecular weight of polyethylene that generally adopts the Ziegler-Natta catalyst polymerization to obtain is distributed in 4 to 8 left and right.

Sequence number 1 and 3 in contrast table 1, sequence number 2 and 4 test-results data are as can be known, after copolymerization, catalyst activity has greatly to be increased, thereby explanation adopts the load type non-metallocene catalyst of method preparation provided by the invention to have comparatively significant comonomer effect.

By sequence number 1 in contrast table 1 and reference example sequence number 14,15 test-results data as can be known, increase or reduce the add-on of Nonmetallocene part in catalyzer, its activity increases thereupon or reduces, and the molecular weight distribution of polymkeric substance also narrows down thereupon or broadens.Reduce in catalyzer or increase chemical processing agent, its activity decreases or increases, and the molecular weight distribution of polymkeric substance also narrows down thereupon or broadens.thereby illustrate that the Nonmetallocene part plays a part the molecular weight distribution that narrows in load type non-metallocene catalyst component provided by the present invention, and in contrast table 1 sequence number 1 and 16 test-results data are as can be known, it is lower that complex carrier processes without chemical processing agent the catalyst activity that obtains, and the molecular weight distribution that obtains thus is narrower, chemical processing agent therefore provided by the present invention is processed the method for complex carrier, its part and Nonmetallocene part original position generate Nonmetallocene title complex component, has the effect that improves catalyst activity and broadening molecular weight distribution.Therefore the researcher in this field knows, can obtain the catalyzer of different activities and polymer performance by the proportioning that changes both.

test-results data by sequence number 1 in contrast table 1 and reference example sequence number 17 as can be known, under the substantially similar catalyzer preparation condition identical with polymerization, be dissolved at magnesium compound and introduce alcohol in the first dissolving agent process, although can increase catalyst activity and polymer stacks density, but therefore molecular weight distribution broadens, those skilled in the art will know that, the non-metallocene catalyst characteristic is that polymericular weight is narrowed down, this just illustrates and the existence of having confirmed the alcohol of mentioning in the background technology can affect or weaken the performance of non-metallocene catalyst intrinsic performance, also embodied from another point of view technology of the present invention creative.

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

Claims

Make the chemical processing agent and optional porous support reaction through thermal activation treatment, the step that obtains to modify carrier that are selected from IVB family metallic compound;

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

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

Wherein said the first solvent is selected from one or more in C6-12 aromatic hydrocarbon, halo C6-12 aromatic hydrocarbon, ester and ether.

2. according to preparation method claimed in claim 1, also be included in make described chemical processing agent and the reaction of described complex carrier before, with the step that helps the described complex carrier of chemical processing agent pre-treatment that is selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

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

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

5. according to preparation method claimed in claim 4, it is characterized in that, described porous support is silicon-dioxide.

6. 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.

7. according to preparation method claimed in claim 6, it is characterized in that, described magnesium compound is selected from one or more in magnesium halide.

8. according to preparation method claimed in claim 7, it is characterized in that, described magnesium compound is magnesium chloride.

9. according to preparation method claimed in claim 1, it is characterized in that, described the first solvent is selected from one or more in C6-12 aromatic hydrocarbon and tetrahydrofuran (THF).

10. according to preparation method claimed in claim 9, it is characterized in that, described the first solvent is tetrahydrofuran (THF).

11. according to preparation method claimed in claim 1, it is characterized in that, described the second solvent is selected from one or more in C6-12 aromatic hydrocarbon, halo C6-12 aromatic hydrocarbon, halogenated alkane and ether.

12. according to the described preparation method of claim 11, it is characterized in that, described the second solvent is selected from one or more in C6-12 aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).

13. according to the described preparation method of claim 12, it is characterized in that, described the second solvent is tetrahydrofuran (THF).

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

In above chemical structural formula,

Q is 0 or 1;

D is 0 or 1;

A be selected from Sauerstoffatom, sulphur atom, selenium atom,

-NR ²³R ²⁴,-N (O) R ²⁵R ²⁶,

-N (O) R ²⁵R ²⁶,

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

R ¹To R ³, R ²²To R ³³And 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,

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

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

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

In above all chemical structural formulas,

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

16. according to the described preparation method of claim 15, it is characterized in that, described Nonmetallocene part is selected from one or more in to compound (A-4) and compound (B-1) to compound (B-4) of 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, contain seleno group or phosphorus-containing groups; Work as R ⁵For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R ⁵In N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center IVB family atoms metal.

17. according to the described preparation method of claim 14-16 any one, 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 oxy radical be selected from hydroxyl ,-OR ³⁴With-T-OR ³⁴

Wherein, described silicon-containing group is selected from-SiR ⁴²R ⁴³R ⁴⁴Or-T-SiR ⁴⁵Described germanic group is selected from-GeR ⁴⁶R ⁴⁷R ⁴⁸Or-T-GeR ⁴⁹Describedly contain tin group and be selected from-SnR ⁵⁰R ⁵¹R ⁵²,-T-SnR ⁵³Or-T-Sn (O) R ⁵⁴

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

Described group T ditto defines.

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

19. according to the described preparation method of claim 18, it is characterized in that, described Nonmetallocene part is selected from one or more in the compound with following chemical structural formula:

20. according to preparation method claimed in claim 1, it is characterized in that, take the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part as 1: 0.0001-1, the ratio of described magnesium compound and described the first solvent is 1mol: 75～400ml, take the mass ratio of the described magnesium compound of magnesium compound solid and described porous support as 1: 0.1-20, the volume ratio of described precipitation agent and described the first solvent is 1: 0.2～5, and in the described magnesium compound of Mg element with take the mol ratio of the described chemical processing agent of IVB family metallic element respectively independently of one another as 1: 0.01-1.

21. according to the described preparation method of claim 20, it is characterized in that, take the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part as 1: 0.0002-0.4, the ratio of described magnesium compound and described the first solvent is 1mol: 150～300ml, take the mass ratio of the described magnesium compound of magnesium compound solid and described porous support as 1: 0.5-10, the volume ratio of described precipitation agent and described the first solvent is 1: 0.5～2, and in the described magnesium compound of Mg element with take the mol ratio of the described chemical processing agent of IVB family metallic element respectively independently of one another as 1: 0.01-0.50.

22. according to the described preparation method of claim 21, it is characterized in that, take the mol ratio of the described magnesium compound of Mg element and described Nonmetallocene part as 1: 0.001-0.1, the ratio of described magnesium compound and described the first solvent is 1mol: 200～250ml, take the mass ratio of the described magnesium compound of magnesium compound solid and described porous support as 1: 1-5, the volume ratio of described precipitation agent and described the first solvent is 1: 0.8～1.5, and in the described magnesium compound of Mg element with take the mol ratio of the described chemical processing agent of IVB family metallic element respectively independently of one another as 1: 0.10-0.30.

23. according to preparation method claimed in claim 1, it is characterized in that, described precipitation agent is selected from one or more in alkane, naphthenic hydrocarbon, halogenated alkane and halo naphthenic hydrocarbon.

24. according to the described preparation method of claim 23, it is characterized in that, described precipitation agent is 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, the chloro suberane, the chloro cyclooctane, the chloro cyclononane, the chloro cyclodecane, bromocyclopentane, bromocyclohexane, the bromo suberane, the bromo cyclooctane, one or more in bromo cyclononane and bromo cyclodecane.

25. according to the described preparation method of claim 24, it is characterized in that, described precipitation agent is selected from one or more in hexane, heptane, decane and hexanaphthene.

26. according to the described preparation method of claim 25, it is characterized in that, described precipitation agent is hexane.

27. according to preparation method claimed in claim 1, it is characterized in that, described IVB family metallic compound is selected from one or more in IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, IVB family's metal alkyl halides and IVB family metal alkoxide halogenide.

28. according to the described preparation method of claim 27, it is characterized in that, described IVB family metallic compound is selected from one or more in IVB family metal halide.

29. according to the described preparation method of claim 28, it is characterized in that, described IVB family metallic compound is selected from TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄And HfBr ₄In one or more.

30. according to the described preparation method of claim 29, it is characterized in that, described IVB family metallic compound is selected from TiCl ₄And ZrCl ₄In one or more.

31. according to preparation method claimed in claim 2, it is characterized in that, described aikyiaiurnirsoxan beta is selected from one or more in methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide and normal-butyl alumina alkane, and described aluminum alkyls is selected from one or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, three n-butylaluminum, triisopentyl aluminium, three n-pentyl aluminium, three hexyl aluminium, three isohexyl aluminium, diethylmethyl aluminium and dimethyl ethyl aluminium.

32. according to the described preparation method of claim 31, it is characterized in that, described aikyiaiurnirsoxan beta is selected from one or more in methylaluminoxane and isobutyl aluminium alkoxide, and described aluminum alkyls is selected from one or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium.

33. according to preparation method claimed in claim 2, it is characterized in that, in the described magnesium compound of Mg element with the mol ratio that helps chemical processing agent take Al element described as 1: 0-1.0.

34. according to the described preparation method of claim 33, it is characterized in that, in the described magnesium compound of Mg element with the mol ratio that helps chemical processing agent take Al element described as 1: 0-0.5.

35. according to the described preparation method of claim 34, it is characterized in that, in the described magnesium compound of Mg element with the mol ratio that helps chemical processing agent take Al element described as 1: 0.1-0.5.

36. a load type non-metallocene catalyst, it is by making according to the described preparation method of claim 1-35 any one.

37. alkene homopolymerization/copolymerization process, it is characterized in that, take according to the described load type non-metallocene catalyst of claim 36 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.