CN102399320B - Supported non-metallocene catalyst and preparation method and application thereof - Google Patents

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 a non-metallocene complex 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, at some aspect of performance, reach, even surpass metallocene catalyst, become after Ziegler, Ziegler-Natta and metallocene catalyst the 4th generation olefin polymerization catalysis.By the excellent property of the polyolefin products of such catalyzer manufacturing, and low cost of manufacture.Non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and there is cis alkyl or halogen metal division center, easily carry out alkene insertion and σ-key and shift, the easy alkylation of central metal, is conducive to the generation at cation activity center; The title complex forming has the geometric configuration of restriction, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key easily polarizes, and is more conducive to polymerization and the copolymerization of alkene.

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

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

For widening aggregated application scope, meet more polymerization technique process, as vapour phase polymerization or slurry polymerization etc., common way is by certain load technology by non-metallocene catalyst, 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, improve the form of polymkeric substance, improve the apparent density (being bulk density) of polymkeric substance, avoided caking or the cruelly poly-phenomenon in polymerization process to occur.

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

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

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

Patent 200910180601.4 and 200910180606.7 is the preparation method of disclosed a kind of load type non-metallocene catalyst respectively, it is that magnesium compound and Nonmetallocene title complex are dissolved in solvent, add after the porous support of thermal activation treatment dry or add precipitation agent after filtration washing dry, obtain 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 surface, follow-up load non-metallocene metal complexes is had a negative impact, limited its active performance.

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

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 obtains thus.

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 obtaining, or the modification magnesium compound that adopts magnesium compound-tetrahydrofuran (THF)-ol to obtain is after precipitation carrier, by various combination, successively contact with active metallic compound with Nonmetallocene part, and the original position load completing.Because magnesium compound is as single carrier, cause catalyzer physical strength low, in polymerization process, easily form fine polymer powder, affected the steady running of polymerization production device.

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

Patent CN200710162666.7 discloses loaded catalyst, load type non-metallocene catalyst and preparation method thereof, it is to have under alcohol existence, magnesium compound is dissolved in tetrahydrofuran solvent, add porous support, after convection drying with titanium tetrachloride reaction, last load non-metallocene metal complexes again, catalyst activity is higher, and the polymkeric substance that polymerization obtains thus has high bulk density, comparatively complicated owing to forming, especially the existence of alcohol, can exert an influence to the performance of Nonmetallocene title complex intrinsic performance.

In order to improve load type non-metallocene catalyst activity, patent 200410066068.6, and the patent PCT/CN2005/001737 applying for based on it discloses high activity loading method and a kind of carry type non-metallocene calalyst for polymerization of olefine, its preparation method and the application thereof of non-metallocene catalyst.It is by adopting IVB family metallic compound to process porous support, then join that alcohol exists with magnesium compound tetrahydrofuran solution, after after filtration washing is dry, optional JingIVB family metallic compound is processed, final load Nonmetallocene title complex.This process still has the existence of alcohol, and filtration washing process can exert an influence to the composition control of final catalyzer.

Even so, the ubiquitous problem of load type non-metallocene catalyst existing in prior art is, load process is complicated, generally need to carry out the multistep of carrier and process afterwards load non-metallocene metal complexes again, olefin polymerizating activity is low and be difficult to regulate, and in order to improve its polymerization activity, preparation process needs the existence of alcohol, must assist higher promotor consumption when carrying out olefinic polymerization.For the carrier loaded non-metallocene catalyst of porous support list, carrier need be after thermal activation treatment be processed with the chemical reagent that aluminum alkyls etc. reacts with it again, and needs the strict preparation condition of controlling for the carrier loaded non-metallocene catalyst of magnesium compound list.

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

Summary of the invention

The inventor finds through diligent research on the basis of existing technology, by manufacturing described load type non-metallocene catalyst by a kind of specific preparation method, in order to solve foregoing problems, and has completed 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 using) etc., reaction requirement and reaction conditions that also need not be harsh.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.

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

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

The chemical processing agent that is selected from IV B family metallic compound is reacted with the optional porous support through thermal activation treatment, obtain the step of modifying carrier;

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;

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

The chemical processing agent that makes to be selected from described IV B family metallic compound reacts with described complex carrier, obtains the step of modifying complex carrier;

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

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

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

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

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

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

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

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

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from periodic table of elements Ⅲ Zu DaoⅪ family atoms metal, preferably Ⅳ B family atoms metal, more preferably Ti (IV) and Zr (IV);

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

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

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

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

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

D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C ₁-C ₃₀alkyl, sulfuryl, sulfoxide group, -N (O) R ²⁵r ²⁶,

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

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

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

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

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

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

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

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

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

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

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

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

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

Described phosphorus-containing groups is selected from

-PR ²⁸r ²⁹,-P (O) R ³⁰r ³¹or-P (O) R ³²(OR ³³);

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

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

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

Described group T is selected from C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl or 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 contains 1-3 heteroatoms that is selected from nitrogen-atoms, Sauerstoffatom or sulphur atom;

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

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 or nitro,

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

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

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

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

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

Described Ar represents C ₆-C ₃₀aryl, and

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

8. according to the preparation method described in aforementioned either side, it is characterized in that, take the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene title complex is 1: 0.01-1, preferably 1: 0.04-0.4, more preferably 1: 0.08-0.2, the ratio of described magnesium compound and described the first solvent is 1mol: 75～400ml, preferred 1mol: 150～300ml, more preferably 1mol: 200～250ml, take the described magnesium compound of magnesium compound solid and the mass ratio of described porous support is 1: 0.1-20, preferably 1: 0.5-10, more preferably 1: 1-5, the volume ratio of described precipitation agent and described the first solvent is 1: 0.2～5, preferably 1: 0.5～2, more preferably 1: 0.8～1.5, and the mol ratio of the described chemical processing agent that the described magnesium compound Yu YiⅣ B family metallic element of Mg element of take is counted is respectively 1 independently of one another: 0.01-1, preferably 1: 0.01-0.50, more preferably 1: 0.10-0.30.

9. according to the preparation method described in 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, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, one or more in bromo cyclononane and bromo cyclodecane, further be preferably selected from hexane, heptane, one or more in decane and hexanaphthene, hexane most preferably.

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

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

13. 1 kinds of load type non-metallocene catalysts, it is to be manufactured by the preparation method according to described in aspect 1-12 any one.

14. 1 kinds of alkene homopolymerization/copolymerization process, it is characterized in that, take according to the load type non-metallocene catalyst described in aspect 13 is Primary Catalysts, take that to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt be promotor, make alkene homopolymerization or copolymerization.

15. 1 kinds of alkene homopolymerization/copolymerization process, is characterized in that, comprise the following steps:

According to the preparation method described in aspect 1-12 any one, manufacture load type non-metallocene catalyst, and

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

Technique effect

Load type non-metallocene catalyst preparation method technique prepared by method provided by the invention is 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.

Adopt method for preparing catalyst provided by the invention, because complex carrier fully precipitates dry rear the obtaining of rear filtration washing under precipitation agent effect by mixed slurry, so in catalyzer, the combination of key substance is comparatively tight.

When the load type non-metallocene catalyst that employing the present invention obtains and promotor form catalyst system, show significant comonomer effect during copolymerization,, 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 title complex consumption, 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 to catalyzer and polymer performance, regulate with the preparation process of the add-on of chemical processing agent.

Embodiment

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

The preparation method who the present invention relates to a kind of load type non-metallocene catalyst, comprises the following steps: the chemical processing agent that is selected from IV B family metallic compound is reacted with the optional porous support through thermal activation treatment, obtain the step of modifying carrier; 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; In described the first mixed serum, add precipitation agent, obtain the step of complex carrier; The chemical processing agent that makes to be selected from described IV B family metallic compound reacts with described complex carrier, obtains the step of modifying complex carrier; Nonmetallocene title complex is contacted under the existence of the second solvent with described modification complex carrier, obtain the step of the second mixed serum; With the second mixed serum described in convection drying, obtain the step of described load type non-metallocene catalyst.

Below described porous support is specifically described.

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

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

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

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

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

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

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

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

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

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

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

Below described chemical processing agent is specifically described.

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

As described IV B family metallic compound, such as enumerating metal alkyl halides HeⅣ B family of metal alkoxide compound ,Ⅳ B family of metal alkyl compound ,Ⅳ B family of metal halide ,Ⅳ B family of 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 enumerating the compound of 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 periodic table of elements ZhongⅣ B family metal, such as titanium, zirconium and hafnium etc.;

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

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

Particularly, as described 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 separately a kind of, or is used in combination multiple with ratio arbitrarily.

According to the present invention, the chemical processing agent that makes to be selected from described IV B family metallic compound react with the described optional porous support through thermal activation treatment, obtains and modifies carrier (reacting I hereinafter referred to as chemical treatment); Or the chemical processing agent that makes to be selected from described IV B family metallic compound reacts with complex carrier as described below, obtains and modifies 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 used 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 directly dripping the mode of the described chemical processing agent of predetermined amount in the reaction object to needing to utilize this chemical processing agent to process (such as the described optional porous support through thermal activation treatment or complex carrier as described below, as follows).

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

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

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

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

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

As carrying out described chemically treated method, such as enumerating, in the situation that adopting solid chemical processing agent (such as zirconium tetrachloride), first the solution of preparing described chemical processing agent, then to the described chemical processing agent that adds (preferably dripping) predetermined amount in pending reaction object (such as described optional porous support through thermal activation treatment or complex carrier as described below); In the situation that adopting 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 (preferably dripping) pending reaction object (such as the described optional porous support through thermal activation treatment or complex carrier as described below), and under the temperature of reaction of-30～60 ℃ (preferably-20～30 ℃), make chemical treatment reaction (if desired by stirring) carry out 0.5～24 hour, preferably 1～8 hour, more preferably 2～6 hours, then filter, wash and be dried.

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

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

Below described magnesium compound is specifically described.

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

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

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

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

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

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

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

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

These magnesium compounds can be used separately a kind of, also can multiple mixing use, not special restriction.

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

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

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

Particularly, described magnesium compound (solid) is dissolved in suitable solvent (for dissolving the solvent of described magnesium compound, or 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 is in preparation during described load type non-metallocene catalyst, in any step, all do not use alcohols (such as aromatic alcohols such as the fatty alcohols such as ethanol, phenylcarbinols etc.) as solvent.

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

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

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

Then,, by described modification carrier is mixed with described magnesium compound solution, 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 under the preparation temperature of described magnesium compound solution, in described magnesium compound solution, be metered into described modification carrier, or be metered into described magnesium compound solution in described modification carrier, mix 0.1～8h, preferred 0.5～4h, optimum 1～2h (if desired by stirring).

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

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 " is used the common concept in this area, refers to and 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, such as enumerating for described magnesium compound, be poor solvent, and for for dissolving for the described solvent of described magnesium compound the solvent for good solvent, 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 preferably 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 separately a kind of, also can use with the multiple mixing of ratio arbitrarily.

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

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

Completely, after precipitation, obtained solid product filtered, washed and is dried, can obtain described complex carrier.For described filtration, washing and dry method, be not particularly limited, can use as required conventional those that use in this area.As required, described washing is generally carried out 1～6 time, preferably 2～3 times.Wherein, washer solvent is preferably used the solvent identical with precipitation agent, but also can be different.

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

Described dry temperature range is generally normal temperature to 100 ℃, and time of drying to be dried until quality of material no longer reduce and be limited.Such as, adopting tetrahydrofuran (THF) as when dissolving the solvent of described magnesium compound, drying temperature is generally 80 ℃ of left and right, under vacuum, be dried 2～12 hours, and adopting toluene as when dissolving the solvent of described magnesium compound, drying temperature is generally 100 ℃ of left and right, under vacuum, is dried 4～24 hours.

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, now just can not select and have the solvent of stripping capacity to dissolve described chemical processing agent to described magnesium compound, 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 non-metallocene olefin polymerization title complex) that can demonstrate olefinic polymerization catalysis activity when combining with aikyiaiurnirsoxan beta, this compound comprises central metal atom and at least one polydentate ligand of being combined with coordinate bond with described central metal atom (preferably tridentate ligand or more polydentate ligand), and term " Nonmetallocene part " is aforesaid polydentate ligand.

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

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

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

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

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

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from periodic table of elements Ⅲ Zu DaoⅪ family atoms metal, preferred Ⅳ B family atoms metal, such as enumerating Ti (IV), Zr (IV), Hf (IV), Cr (III), Fe (III), Ni (II), Pd (II) or Co (II);

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

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

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

-NR ²³r ²⁴,-N (O) R ²⁵r ²⁶,

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

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

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

-N (O) R ²⁵r ²⁶,

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

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

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

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

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

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

R ¹to R ⁴, R ⁶to R ³⁶, R ³⁸and R ³⁹be selected from independently of one another hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl (preferred halo alkyl wherein, such as-CH ₂cl and-CH ₂cH ₂cl) or safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group is such as R ¹with R ², R ⁶with R ⁷, R ⁷with R ⁸, R ⁸with R ⁹, R ¹³with R ¹⁴, R ¹⁴with R ¹⁵, R ¹⁵with R ¹⁶, R ¹⁸with R ¹⁹, R ¹⁹with R ²⁰, R ²⁰with R ²¹, R ²³with R ²⁴, or R ²⁵with R ²⁶deng combining togather into key or Cheng Huan, be preferably formed aromatic ring, such as unsubstituted phenyl ring or by 1-4 C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl (preferred halo alkyl wherein, such as-CH ₂cl and-CH ₂cH ₂cl) or the phenyl ring that replaces of safing function group, and

R ⁵be selected from lone-pair electron on nitrogen, hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R ⁵during for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups, R ⁵in N, O, S, P and Se can be used as coordination and carry out coordination with atom and described center 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, such as R ²¹with group Z, or R ¹³with group Y, can combine togather into ring, be preferably formed and comprise the heteroatomic C that comes from described group Z or Y ₆-C ₃₀heteroaromatic, such as pyridine ring etc., wherein said heteroaromatic is optionally selected from C by one or more ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀the substituting group of alkyl and safing function group replaces.

In the context of the present invention,

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

Described nitrogen-containing group is selected from

-NR ²³r ²⁴,-T-NR ²³r ²⁴or-N (O) R ²⁵r ²⁶;

Described phosphorus-containing groups is selected from

-PR ²⁸r ²⁹,-P (O) R ³⁰r ³¹or-P (O) R ³²(OR ³³);

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

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

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

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

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

In the context of the present invention, the C of described replacement ₁-C ₃₀alkyl refers to the aforementioned C with one or more inert substituents ₁-C ₃₀alkyl.So-called inert substituent, refer to these substituting groups to aforementioned for coordination group (refer to aforementioned group A, D, E, F, Y and Z, or also optionally comprise radicals R ⁵) there is no substantial interference with the coordination process of described central metal atom M; In other words, limit by the chemical structure of polydentate ligand of the present invention, these substituting groups do not have ability or have no chance (such as being subject to the impact of steric hindrance etc.) coordination reaction occurs and form coordinate bond with described central metal atom M.Generally speaking, described inert substituent refers to aforementioned halogen or C ₁-C ₃₀alkyl (preferred C ₁-C ₆alkyl, such as isobutyl-).

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

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

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

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

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

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

Described Nonmetallocene title complex is preferably selected from following compound:

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

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

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

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

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

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

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

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

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

According to the present invention, when manufacturing described the second mixed serum, to described the second solvent (be sometimes referred to as below and dissolve Nonmetallocene title complex solvent), there is no particular limitation, the magnesium compound described in not stripping as long as it can dissolve described Nonmetallocene title complex.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).

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

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

According to the present invention, to the consumption of described the second solvent without any restriction, so long as be enough to realize the amount that described modification complex carrier fully contacts with described Nonmetallocene title complex.Such as, easily, described Nonmetallocene title complex is generally 0.01～0.25 grams per milliliter with respect to the ratio of described the second solvent, preferred 0.05～0.16 grams per milliliter, but be sometimes not limited to this.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As carrying out described pretreated method, such as enumerating, first described in preparing, help the solution of chemical processing agent, then at the temperature of-30～60 ℃ (preferably-20～30 ℃), to intend with described in help in the pretreated described complex carrier of chemical processing agent to be metered into and help chemical treatment agent solution (contain predetermined amount described in help chemical processing agent) described in (preferably dripping), or 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, 3～4h (if desired by stir) most preferably.Then, obtained pre-treatment product process is filtered, washed (1～6 time, preferably 1～3 time) and optionally drying, and separate from this reaction mixture, or, also can be without this separation and be directly used in follow-up reactions steps with the form of mixed solution.Now, owing to having contained a certain amount of solvent in described mixed solution, so the solvent load relating in can the described subsequent reactions step of corresponding minimizing.

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 to the pretreated complex carrier of described process.; by reacting II with aforementioned same chemical treatment; the chemical processing agent that makes to be selected from described IV B family metallic compound reacts to manufacture modification complex carrier with the pretreated complex carrier of described process, and further utilizes this modification complex carrier according to manufacturing load type non-metallocene catalyst of the present invention with same before mode.

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

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

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

According to the present invention, 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 each chemical treatment reaction, to reach independently of one another 1 in the mol ratio of the described chemical processing agent of described magnesium compound (solid) Yu YiⅣ B family's metal (such as Ti) element meter of Mg element: 0.01-1, preferably 1: 0.01-0.50, more preferably 1: 0.10-0.30.

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

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

Known to those skilled in the art, aforementioned all method stepss all preferably carry out under the condition of anhydrous anaerobic substantially.Here said anhydrous anaerobic substantially refers to the content of water and oxygen in system and continues to be less than 10ppm.And load type non-metallocene catalyst of the present invention needs pressure-fired in confined conditions to save backup in preparation afterwards conventionally.

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

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

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

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

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

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

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

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

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

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

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

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

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

Al(R) ₃ (III-1)

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

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

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

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

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

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

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

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

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

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

Embodiment

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

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

The content of load type non-metallocene catalyst ZhongⅣ B family's metal (such as Ti) and Mg element adopts 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 is dried, then weigh the quality of this polymerisate, with this polymerisate quality, divided by the ratio of the quality of load type non-metallocene catalyst used, represent the polymerization activity (unit is kg polymkeric substance/g catalyzer or kg polymkeric substance/gCat) of this catalyzer.

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

Embodiment 1

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

Chemical processing agent adopts titanium tetrachloride (TiCl ₄).Take the silica gel after 5g thermal activation, add 60ml hexane, under stirring at normal temperature condition, add titanium tetrachloride, at 60 ℃, react after 2h, 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.Nonmetallocene title complex adopts structure to be

compound.

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

Then in described complex carrier, add 60ml hexane, under agitation condition, with 30 minutes, drip titanium tetrachloride, at 60 ℃, stirring reaction is 4 hours, filter, and hexane washing 2 times, each hexane consumption 60ml, under normal temperature, vacuum-drying obtains modifying complex carrier.

Take described nonmetal title complex, be dissolved in completely in the second solvents tetrahydrofurane, disposablely add described modification complex carrier, stir 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 described magnesium compound of Mg element and the mol ratio of Nonmetallocene title complex is 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 described magnesium compound of magnesium compound solid and the mass ratio of porous support is 1: 2, and 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 have following change:

Before chemical processing agent is processed 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 to help the mol ratio of chemical processing agent methylaluminoxane be 1: 0.3.

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

Embodiment 3

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

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

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

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

Embodiment 4

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

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

Nonmetallocene title complex 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 described magnesium compound of Mg element and the mol ratio of Nonmetallocene title complex is 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 described magnesium compound of magnesium compound solid and the mass ratio of porous support is 1: 1, and 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 have following change:

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

Magnesium compound is changed into anhydrous magnesium bromide (MgBr ₂), Nonmetallocene title complex 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 described magnesium compound of Mg element and the mol ratio of Nonmetallocene title complex is 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 described magnesium compound of magnesium compound solid and the mass ratio of porous support is 1: 5, and 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 have following change:

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

Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC ₂h ₅)), Nonmetallocene title complex 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 described magnesium compound of Mg element and the mol ratio of Nonmetallocene title complex is 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 described magnesium compound of magnesium compound solid and the mass ratio of porous support is 1: 0.5, and 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 have following change:

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

Magnesium compound is changed into butoxy magnesium bromide (MgBr (OC ₄h ₉)), Nonmetallocene title complex 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 have following change:

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

Magnesium compound is changed into methylmagnesium-chloride (Mg (CH ₃) Cl), Nonmetallocene title complex 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 have following change:

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

Magnesium compound is changed into magnesium ethide (Mg (C ₂h ₅) ₂), Nonmetallocene title complex 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 have following change:

Do not add Nonmetallocene title complex.

Catalyzer is designated as CAT-1-A.

Reference example 1-B

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

Take the described magnesium compound of Mg element and the mol ratio of Nonmetallocene title complex is 1: 1;

Catalyzer is designated as CAT-1-B.

Reference example 1-C

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

Take the described magnesium compound of Mg element and the mol ratio of Nonmetallocene title complex is 1: 0.25;

Catalyzer is designated as CAT-1-C.

Reference example 1-D

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

Complex carrier is processed without titanium tetrachloride.

Catalyzer is designated as CAT-1-D.

Embodiment 10 (Application Example)

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

Homopolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture (promotor Yu Yi IVB family metal meter load type non-metallocene catalyst mol ratio is 100: 1), add again hydrogen to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction finishes, by gas reactor emptying, emit still interpolymer, the dry rear quality that weighs.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.

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

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

Known by testing result data in table 1, the load type non-metallocene catalyst that adopts method provided by the invention to prepare has 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 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 known, after copolymerization, catalyst activity has greatly to be increased, thereby the load type non-metallocene catalyst that explanation adopts method provided by the invention to prepare has comparatively significant comonomer effect.

Test-results data by sequence number 1 in contrast table 1 and reference example sequence number 14,15 are known, increase or reduce the add-on of Nonmetallocene title complex in catalyzer, and its activity increases thereupon or reduces, and the molecular weight distribution of polymkeric substance also narrows down thereupon or broadens.In catalyzer, reduce 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 Nonmetallocene title complex has the effect of the molecular weight distribution of narrowing, and in contrast table 1 sequence number 1 and 16 test-results data known, it is lower that complex carrier processes without chemical processing agent the catalyst activity obtaining, and the molecular weight distribution obtaining is thus narrower, chemical processing agent therefore provided by the present invention is processed the method for complex carrier, has the effect that improves catalyst activity and broadening molecular weight distribution.Therefore researcher in this field knows, can obtain the catalyzer of different activities and polymer performance by the proportioning that changes both.

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

Claims (35)

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

The chemical processing agent that is selected from IV B family metallic compound is reacted with the optional porous support through thermal activation treatment, obtain the step of modifying carrier;

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;

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

The chemical processing agent that makes to be selected from described IV B family metallic compound reacts with described complex carrier, obtains the step of modifying complex carrier;

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

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

2. according to preparation method claimed in claim 1, be also included in and make before described chemical processing agent reacts with described complex carrier, by the step that helps complex carrier described in 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, the partial cross-linked form of these homopolymer or multipolymer, periodic table of elements IIA, IIIA, refractory oxide or the infusibility composite oxides of IV A HuoⅣ B 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, halo C6-12 aromatic hydrocarbon, ester and ether, 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.

10. according to preparation method claimed in claim 9, 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).

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

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

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

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

In above chemical structural formula,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from Dao XI family of periodic table of elements 1II family atoms metal;

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

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

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

-NR ²³r ²⁴,-N (0) 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 or sulfoxide group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

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

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

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

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

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

Described nitrogen-containing group is selected from

-NR ²³r ²⁴,-T-NR ²³r ²⁴or-N (O) R ²⁵r ²⁶;

Described phosphorus-containing groups is selected from

-PR ²⁸r ²⁹,-P (O) R ³⁰r ³¹or-P (O) R ³²(OR ³³);

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

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

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

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

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

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

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

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

Describedly be selected from aluminum alkyls, AlPh containing aluminium base group ₄ ^-, AlF ₄ ^-, A1C1 ₄ ^-, AlBr ₄ ^-, All ₄ ^-or R ⁴¹alAr ₃ ^-;

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

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

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

Described Ar represents C ₆-C ₃₀aryl, and

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

And described group T ditto defines.

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

In above all chemical structural formulas,

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

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

In above all chemical structural formulas,

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

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

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

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

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

18. according to the preparation method described in claim 17, it is characterized in that, described Nonmetallocene title complex is selected from one or more in the compound with following chemical structural formula:

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

20. according to the preparation method described in claim 19, it is characterized in that, take the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene title complex is 1:0.04-0.4, the ratio of described magnesium compound and described the first solvent is 1mol:150～300ml, take the described magnesium compound of magnesium compound solid and the mass ratio of described porous support is 1:0.5-10, the volume ratio of described precipitation agent and described the first solvent is 1:0.5～2, and the mol ratio of the described chemical processing agent that the described magnesium compound Yu YiⅣ B family metallic element of Mg element of take is counted is respectively 1:0.01-0.50 independently of one another.

21. according to the preparation method described in claim 20, it is characterized in that, take the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene title complex is 1:0.08-0.2, the ratio of described magnesium compound and described the first solvent is 1mol:200～250ml, take the described magnesium compound of magnesium compound solid and the mass ratio of described porous support is 1:1-5, the volume ratio of described precipitation agent and described the first solvent is 1:0.8～1.5, and the mol ratio of the described chemical processing agent that the described magnesium compound Yu YiⅣ B family metallic element of Mg element of take is counted is respectively 1:0.10-0.30 independently of one another.

22. 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.

23. according to the preparation method described in claim 22, 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, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, one or more in bromo cyclononane and bromo cyclodecane.

24. according to the preparation method described in claim 23, it is characterized in that, described precipitation agent is hexane.

25. according to preparation method claimed in claim 1, it is characterized in that, described IV B family metallic compound is selected from one or more in metal alkyl halides HeⅣ B family of metal alkoxide compound ,Ⅳ B family of metal alkyl compound ,Ⅳ B family of metal halide ,Ⅳ B family of IV B family metal alkoxide halogenide.

26. according to the preparation method described in claim 25, it is characterized in that, described IV B family metallic compound is selected from one or more in IV B family metal halide.

27. according to the preparation method described in claim 26, it is characterized in that, described IV B family metallic compound is selected from TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfC1 ₄and HfBr ₄in one or more.

28. according to the preparation method described in claim 27, it is characterized in that, described IV B family metallic compound is selected from TiCl ₄and ZrCl ₄in one or more.

29. 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.

30. according to the preparation method described in claim 29, it is characterized in that, described aikyiaiurnirsoxan beta is selected from one or more in methylaluminoxane and isobutyl aluminium alkoxide.

31. according to the preparation method described in claim 29, it is characterized in that, described aluminum alkyls is selected from one or more in trimethyl aluminium, triethyl aluminum, tri-propyl aluminum and triisobutyl aluminium.

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

33. according to the preparation method described in claim 32, it is characterized in that, in the described magnesium compound of Mg element with take Al element described in help the mol ratio of chemical processing agent as 1:0.1-0.5.

34. 1 kinds of load type non-metallocene catalysts, it is to be manufactured by the preparation method according to described in claim 1-33 any one.

35. 1 kinds of alkene homopolymerization/copolymerization process, it is characterized in that, take according to the load type non-metallocene catalyst described in claim 34 is Primary Catalysts, take that to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt be promotor, make alkene homopolymerization or copolymerization.