CN102399315B - Supported non-metallocene catalyst and preparation method and use thereof - Google Patents

Abstract

The invention relates to a supported non-metallocene catalyst and its preparation method. The preparation method of the supported non-metallocene catalyst is an in-situ preparation method, is simple, is easy for operation, realizes control on non-metallocene content and has an obvious copolymerization effect. The invention also relates to a use of the supported non-metallocene catalyst in alkene homopolymerization/copolymerization. Compared with the prior art, the use of supported non-metallocene catalyst has the characteristics of high alkene catalysis activity, high polymer bulk density andcontrollable molecular weight distribution.

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

The non-metallocene catalyst that middle and later periods nineteen nineties occurs, claim luxuriant rear catalyst again, the central atom of Primary Catalysts has comprised nearly all transition metal, reach at some aspect of performance, even surpass metallocene catalyst, become after Ziegler, Ziegler-Natta and metallocene catalyst the 4th generation olefin polymerization catalysis.By the excellent property of the polyolefin products of such catalyzer manufacturing, and low cost of manufacture.The non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, do not contain cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and have cis alkyl or halogen metal division center, carry out alkene insertion and σ-key easily and shift, the easy alkylation of central metal is conducive to the generation at cation activity center; The title complex that forms has the geometric configuration of restriction, stereoselectivity, electronegativity and chirality controllability, and in addition, formed metal-carbon key polarizes easily, more is conducive to polymerization and the copolymerization of alkene.Therefore, even under higher polymeric reaction temperature, also can obtain the olefin polymer of higher molecular weight.

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

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

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

At 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 multiple mode to carry out load to obtain load type non-metallocene catalyst.But these patents all relate on the carrier after the Nonmetallocene organic compound that will contain transition metal is carried on processing, and catalyst preparation process is comparatively complicated.

The catalyzer that with the Magnesium Chloride Anhydrous is carrier demonstrates advantages of high catalytic activity in olefin polymerization process, but this type of catalyst strength is poor, and is broken easily in polymerization reactor, thereby causes polymer morphology bad.Silicon dioxide carried catalyzer has good flowability, can be used for slurry polymerization and gas fluidised bed polymerisation, but simple silicon dioxide carried metallocene and non-metallocene catalyst then show lower catalytic activity.Therefore if magnesium chloride and silicon-dioxide are well organically combined, just may prepare and have high catalytic activity, the catalyzer of the controlled and good abrasion strength resistance of globule size.

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

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

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

Chinese patent 200910180100.6,200910180607.1,200910210988.3,200910210984.5,200910210987.9,200910210991.5 disclosed load type non-metallocene catalyst preparation methods and above-mentioned patent are similar, what all use is the thermal activation treatment porous support of crossing and the magnesium compound solution reaction that contains Nonmetallocene part or Nonmetallocene title complex, react with the chemical processing agent that contains IVB family metallic compound more at last, obtain load type non-metallocene catalyst.

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

Patent 200910180603.3,200910180604.8,200910210989.8,200910210986.4,200910210985.X, 200910210990.0 disclosed load type non-metallocene catalyst preparation methods and above-mentioned patent are similar, what all use is that magnesium compound is as carrier, still exist the particle form of catalyzer to be difficult to control, limited the polymer beads form that polymerization thus obtains.

Above patent all relates on the carrier after the Nonmetallocene organometallic compound that will contain transition metal is carried on processing, and because the carrier reaction bonded at non-metallocene catalyst and place is limited, the Nonmetallocene organic compound mainly is to exist with the physical adsorption attitude in the load type non-metallocene catalyst that obtains, and is unfavorable for the control of polymer beads form and the performance of non-metallocene catalyst performance.

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

Even so, the ubiquitous problem of the load type non-metallocene catalyst that exists in the prior art is load process complexity.For the carrier loaded non-metallocene catalyst of porous support list, carrier needs after thermal activation treatment to handle with the chemical reagent of its reaction with aluminum alkyls etc. again, need strict control preparation condition for the carrier loaded non-metallocene catalyst of magnesium compound list, these two kinds of methods all are difficult to obtain good form polymkeric substance by olefinic polymerization.And the Nonmetallocene title complex is carried on the carrier, and part Nonmetallocene title complex is to pile up on carrier with physical adsorption way, both bonding forces a little less than, the Nonmetallocene title complex takes place and comes off and produce fine powder in polymerization process easily.And the composite carrier load non-metallocene catalyst that forms for porous support and magnesium compound, such as Chinese patent 200410066068.6, and based on load method and a kind of carry type non-metallocene calalyst for polymerization of olefine, its preparation method and the application thereof of the disclosed a kind of high reactivity non-metallocene catalyst of the patent PCT/CN2005/001737 of its application, because the existence of alcohol in the system, can have a negative impact to load Nonmetallocene title complex performance thereon, limit giving full play to of Nonmetallocene title complex intrinsic performance.

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

Summary of the invention

The inventor makes described load type non-metallocene catalyst on the basis of existing technology through diligent discovering by using a kind of specific preparation method, in order to solving foregoing problems, and has finished the present invention thus.

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

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

1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:

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

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

Described modification carrier, described magnesium compound solution are contacted with the Nonmetallocene part, obtain the step of mixed serum;

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

Make the chemical processing agent and the reaction of described complex carrier that are selected from described IV B family metallic compound, obtain the step of described load type non-metallocene catalyst.

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

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

4. according to the described preparation method of aforementioned either side, it is characterized in that described solvent is selected from C _6-12Aromatic hydrocarbon, halo C _6-12In aromatic hydrocarbon, ester and the ether one or more are preferably selected from C _6-12In aromatic hydrocarbon and the tetrahydrofuran (THF) one or more, most preferably tetrahydrofuran (THF).

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

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

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

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

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

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

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

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

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

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

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

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

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

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

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

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

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

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

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

Described nitrogen-containing group is selected from

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

Described phosphorus-containing groups is selected from

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

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

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

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

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

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

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

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

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

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

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

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

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

10. load type non-metallocene catalyst, it is by making according to each described preparation method of aspect 1-9.

11. alkene homopolymerization/copolymerization process, it is characterized in that, being Primary Catalysts according to aspect 10 described load type non-metallocene catalysts, be promotor to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more, make alkene homopolymerization or copolymerization.

12. an alkene homopolymerization/copolymerization process is characterized in that, may further comprise the steps:

According to each described preparation method of aspect 1-9 make load type non-metallocene catalyst and

Being Primary Catalysts with described load type non-metallocene catalyst, is promotor to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more, makes alkene homopolymerization or copolymerization.

Technique effect

Preparation method's technology simple possible of load type non-metallocene catalyst of the present invention, the charge capacity of Nonmetallocene component is adjustable, can give full play to itself and chemical processing agent reaction in and generate the Nonmetallocene title complex component with olefinic polymerization catalysis activity, and the performance that obtains polyolefin product at catalysis in olefine polymerization, and the polymerization catalyst activity is higher, and polymer stacks density is also higher.

Adopt method for preparing catalyst provided by the invention, owing to complex carrier is fully obtaining after the post precipitation filtration washing drying under the precipitation agent effect by mixed slurry, so the combination of key substance is comparatively tight in the catalyzer.

Method for preparing catalyst provided by the invention reaches resulting load type non-metallocene catalyst thus, wherein the Nonmetallocene part is after IVB family metallochemistry treatment agent original position is combined, the effect of the molecular weight distribution of narrowing is arranged, and chemical processing agent has the molecular weight distribution of broadening polymkeric substance and the effectiveness of raising polymer stacks density, therefore can come the telomerized polymer structure properties by regulating the relative proportioning with the complex carrier chemical processing agent of Nonmetallocene part, such as molecular weight distribution etc.

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

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 subjected to the restriction of these embodiments, but determined by claims of appendix.

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

Below described porous support is carried out specific description.

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

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

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

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

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

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

According to the present invention, suitable silicon-dioxide can be by the ordinary method manufacturing, it perhaps can be the commerical prod that to buy arbitrarily, such as Grace 955, the Grace948 that can enumerate Grace company, Grace SP9-351, Grace SP9-485, Grace SP9-10046, Davsion Syloid 245 and Aerosil812, the ES70 of Ineos company, ES70X, ES70Y, ES70W, ES757, EP 10X and EP11, and the CS-2133 of Pq Corp. and MS-3040.

Embodiment preferred according to the present invention preferably has hydroxyl isoreactivity functional group on the surface of described inorganic porous solid.

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

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

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

Below described chemical processing agent is carried out specific description.

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

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

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

M(OR ¹) _mX _nR ² _4-m-n (IV)

Wherein:

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

According to the present invention, make the chemical processing agent and the described optional porous support reaction through thermal activation treatment that are selected from described IV B family metallic compound, obtain to modify carrier (hereinafter referred to as chemical treatment reaction I); Perhaps, make the chemical processing agent that is selected from described IV B family metallic compound and complex carrier reaction as described below, obtain load type non-metallocene catalyst of the present invention (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, employed described chemical processing agent can be the same or different separately.

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

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

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

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

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

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

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

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

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

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

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

Below described magnesium compound is carried out specific description.

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

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

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

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

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

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

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

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

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

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

Below the step that obtains described magnesium compound solution is carried out specific description.

Particularly, make described magnesium compound (solid) be dissolved in appropriate solvent (solvent that namely is used for the described magnesium compound of dissolving), thereby obtain described magnesium compound solution.

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

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

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

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

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

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

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

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

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

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

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

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

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

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

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

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

-N (O) R ²⁵R ²⁶,

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

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

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

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

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

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

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

In the context of the present invention,

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

Described nitrogen-containing group is selected from

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

As described Nonmetallocene part, such as enumerating following compound:

Described Nonmetallocene part is preferably selected from following compound:

Described Nonmetallocene part further is preferably selected from following compound:

Described Nonmetallocene part more preferably is selected from following compound:

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

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

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

According to the present invention, described modification carrier, described magnesium compound solution are contacted with described Nonmetallocene part, obtain mixed serum.

When making described mixed serum, there is no particular limitation to the way of contact of described modification carrier, described magnesium compound solution and described Nonmetallocene part and engagement sequence etc., such as enumerating described modification carrier is mixed earlier with described magnesium compound solution, and then to the scheme that wherein adds described Nonmetallocene part; The scheme that described modification carrier, described magnesium compound solution and described Nonmetallocene part are mixed simultaneously; Described Nonmetallocene part and described magnesium compound are dissolved in the foregoing solvent simultaneously, make the mixing solutions (being also referred to as magnesium compound solution hereinafter sometimes) of magnesium compound and Nonmetallocene part thus, and then make scheme that described modification carrier mixes with described mixing solutions etc.

In addition, in order to make described mixed serum, such as can be at normal temperature to the temperature of the boiling point that is lower than employed any solvent, make the contact reacts of described modification carrier, described magnesium compound solution and described Nonmetallocene part carry out 0.1～8h, preferred 0.5～4h, optimum 1～2h (in case of necessity by stirring) gets final product.

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

By in described mixed serum, being metered into precipitation agent, solid matter is precipitated out from this mixed serum, obtain complex carrier thus.

Below described precipitation agent is carried out specific description.

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

According to the present invention, as described precipitation agent, for described magnesium compound, be poor solvent such as enumerating, and for the described solvent that is used for the described magnesium compound of dissolving, be the solvent of 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 preferred hexane, heptane and decane, most preferably hexane.

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

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

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

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

The adding mode of precipitation agent can be disposable adding or dropping, preferred disposable adding.In this precipitation process, can utilize to stir to promote the dispersion of precipitation agent, and be conducive to the final precipitation of solid product.This stirring can be adopted any form, such as stirring rake (rotating speed is generally 10～1000 rev/mins) etc.

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

Post precipitation filters, washs and drying the solid product that obtains fully, obtains complex carrier thus.For described filtration, washing and the dry not special restriction of method, can use conventional those that use in this area as required.

As required, described washing is generally carried out 1～6 time, preferred 2～3 times.Wherein, washer solvent preferably uses the solvent identical with precipitation agent, but also can be different.

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

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

Then, by aforesaid chemical treatment reaction II, make described chemical processing agent and described complex carrier carry out chemical reaction, cause Nonmetallocene part generation coordination reaction contained in described chemical processing agent and this complex carrier, thereby original position generates Nonmetallocene title complex (original position load reaction) on this complex carrier, obtains load type non-metallocene catalyst of the present invention thus.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Particularly, as described C ₂～C ₁₀Monoolefine is such as enumerating ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene and vinylbenzene etc.; As described cyclic olefin, such as enumerating 1-cyclopentenes and norbornylene etc.; As described diolefin, such as enumerating 1,4-divinyl, 2,5-pentadiene, 1,6-hexadiene, norbornadiene and 1,7-octadiene etc.; And as described other ethylenically unsaturated compounds, such as enumerating vinyl acetate and (methyl) acrylate etc.Wherein, the homopolymerization of optimal ethylene, the perhaps copolymerization of ethene and propylene, 1-butylene or 1-hexene.

According to the present invention, homopolymerization refers to only a kind of polymerization of described alkene, and copolymerization refers to the polymerization between the 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 the following general formula (I-1): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the ring-type aikyiaiurnirsoxan beta shown in the following general formula (II-1) :-(Al (R)-O-) _N+2-.

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

As described aikyiaiurnirsoxan beta, preferable methyl aikyiaiurnirsoxan beta, ethyl aikyiaiurnirsoxan beta, 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 alone, and perhaps are used in combination multiple with ratio arbitrarily.

As described aluminum alkyls, such as enumerating the compound shown in the 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 C independently of one another ₁-C ₈Alkyl, preferable methyl, ethyl and isobutyl-, most preferable.

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

These aluminum alkylss can be used alone, and perhaps 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 alone, and also can be as required be used in combination multiple aforesaid promotor, not special restriction with ratio arbitrarily.

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

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

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

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

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

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

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

Embodiment

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

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

The content of IV B family metal (such as Ti) and Mg element adopts the ICP-AES method to measure in the load type non-metallocene catalyst, 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 the reactor is filtered and drying, the quality of this polymerisate of weighing then represents that divided by the ratio of the quality of used load type non-metallocene catalyst (unit is kg polymkeric substance/g catalyzer or kg polymkeric substance/gCat) for the polymerization activity of this catalyzer with this polymerisate quality.

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

Embodiment 1

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

Chemical processing agent adopts titanium tetrachloride (TiCl ₄).Take by weighing the silica gel after the 5g thermal activation, add the 60ml hexane, under the stirring at normal temperature condition, add titanium tetrachloride, at 60 ℃ down behind the reaction 2h, filter, hexane wash 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 and Nonmetallocene part adopts tetrahydrofuran (THF).The Nonmetallocene part adopts structure to be

Compound.

Take by weighing Magnesium Chloride Anhydrous and Nonmetallocene part, dissolve fully under the normal temperature behind the adding tetrahydrofuran solvent and obtain magnesium compound solution, add then and modify carrier, stir after 2 hours, add the precipitation agent hexane then and make it precipitation, filter, wash 2 times, each washing composition consumption evenly is heated under 60 ℃ and vacuumizes drying with add-on is identical before, obtains complex carrier.

Then in this complex carrier, add the 60ml hexane, under agitation condition with 30 minutes dropping titanium tetrachlorides, 60 ℃ of following stirring reactions 4 hours, filter, hexane wash 2 times, each hexane consumption 60ml, vacuum-drying obtains load type non-metallocene catalyst under the normal temperature.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 2; In the Mg element, magnesium compound and Nonmetallocene part mol ratio are 1: 0.08, with the solvents tetrahydrofurane proportioning be 1mol: 240ml, be 1: 0.20 with twice chemical processing agent mol ratio, the volume ratio of precipitation agent and tetrahydrofuran solvent is 1: 1.

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

Embodiment 2

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

Porous support is changed into 955 of Grace company, continues roasting 8h and thermal activation under 400 ℃, nitrogen atmosphere.Chemical processing agent changes zirconium tetrachloride (ZrCl into ₄), hexane changes toluene into.The Nonmetallocene part adopts

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into toluene, and precipitation agent is changed into hexanaphthene.

Then in this complex carrier, add 60ml toluene, under agitation condition with 30 minutes dropping zirconium tetrachlorides, 80 ℃ of following stirring reactions 4 hours, filter, toluene wash 2 times, each toluene consumption 60ml, 60 ℃ of following vacuum-dryings obtain load type non-metallocene catalyst.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 1; In the Mg element, magnesium compound and Nonmetallocene part mol ratio are 1: 0.14, with the solvent toluene proportioning be 1mol: 160ml, be 1: 0.30 twice with the mol ratio of chemical processing agent, the volume ratio of precipitation agent and solvent is 1: 1.5.

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

Embodiment 3

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

Porous support adopts aluminium sesquioxide.Aluminium sesquioxide is continued roasting 6h under 700 ℃, nitrogen atmosphere.Chemical processing agent changes titanium tetrabromide (TiBr into ₄)

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

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into ethylbenzene, and precipitation agent is changed into suberane.

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 4; In the Mg element, magnesium compound and Nonmetallocene part mol ratio are 1: 0.20, with solvent ethylbenzene proportioning be 1mol: 300ml, with the mol ratio of chemical processing agent clearly (successively, I is elder generation with the chemical treatment reaction, after with chemical treatment reaction II being, as follows) be respectively 1: 0.10 and 1: 0.20, the volume ratio of precipitation agent and solvent is 1: 0.6.

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

Embodiment 4

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

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

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

The solvent of dissolved magnesium compound and Nonmetallocene part is 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, magnesium compound and porous support mass ratio are 1: 0.5; In the Mg element, magnesium compound and Nonmetallocene part mol ratio are 1: 0.05, with the solvent xylene proportioning be 1mol: 160ml, successively be respectively 1: 0.70 and 1: 0.10 with the chemical processing agent mol ratio, the volume ratio of precipitation agent and solvent is 1: 0.5.

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

Embodiment 5

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

The porous support adopting montmorillonite.Polynite is continued roasting 8h under 400 ℃, nitrogen atmosphere.Magnesium compound is changed into butoxy magnesium bromide (MgBr (OC ₄H ₉)), the Nonmetallocene part adopts The solvent of dissolved magnesium compound and Nonmetallocene part is changed into diethylbenzene, and precipitation agent is changed into octane-iso, and complex carrier is handled with chemical processing agent and adopted tetra-n-butyl titanium (Ti (C ₄H ₉) ₄).

Wherein proportioning is, magnesium compound and porous support mass ratio are 1: 10, in the Mg element, magnesium compound and Nonmetallocene part mol ratio are 1: 0.4, with solvent diethylbenzene proportioning be 1mol: 120ml, successively be respectively 1: 0.50 and 1: 0.20 with the chemical processing agent mol ratio, the volume ratio of precipitation agent and solvent is 1: 1.3.

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

Embodiment 6

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

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

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

The solvent of dissolved magnesium compound and Nonmetallocene part is changed into chlorotoluene.

Zirconium tetrachloride is adopted in the porous support chemical treatment, and complex carrier is handled and adopted titanium tetrachloride, and in the Mg element, magnesium compound and zirconium tetrachloride mol ratio are 1: 0.30, with the titanium tetrachloride mol ratio be 1: 0.25.

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

Embodiment 7

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

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

Magnesium compound is changed into ethylmagnesium chloride (Mg (C ₂H ₅) Cl), the Nonmetallocene part adopts

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

Reference example 1-A

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

Magnesium compound and Nonmetallocene part mol ratio are changed into 1: 0.16;

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

Reference example 1-B

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

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

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

Reference example 1-C

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

Porous support is handled without chemical processing agent;

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

Reference example 1-D

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

Complex carrier is handled without chemical processing agent;

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

Reference example 1-E

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

Complex carrier obtains by directly mixed serum being vacuumized drying at normal temperatures;

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

Application Example

Load type non-metallocene catalyst CAT-1～7, the CAT-1-A～E that make in the embodiment of the invention are carried out homopolymerization and the copolymerization of ethene respectively under the following conditions in accordance with the following methods:

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

Copolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 rise hexane solvent, polymerization stagnation pressure 0.8MPa, hydrogen partial pressure 0.2MPa, 85 ℃ of polymerization temperatures are 100: 1 in the promotor of aluminium with mol ratio in the load type non-metallocene catalyst of central metal atom, 2 hours reaction times.At first 2.5 liters of hexanes are joined in the polymerization autoclave, open and stir, add 50mg load type non-metallocene catalyst and catalyst mixture then, disposable adding 1-hexene co-monomer 50g and hydrogen continue to feed ethene and make the polymerization stagnation pressure constant in 0.8MPa to 0.2MPa.Reaction with gas reactor emptying, is emitted the still interpolymer after finishing, dry back weighing quality.The particular case of this polyreaction and polymerization evaluation result are as shown in table 1.

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

By table 1 as seen, higher with the load type non-metallocene catalyst polymerization activity of method preparation provided by the invention, and polymer stacks density is higher.

By sequence number 1 in the contrast table 1 and sequence number 10,11 test-results data as can be known, though the Nonmetallocene part does not have the catalysis in olefine polymerization activity, but in catalyst preparation process provided by the invention, increase or reduce Nonmetallocene part add-on, its activity increases thereupon or reduces, and the molecular weight distribution of polymkeric substance also narrows down thereupon and broadens.Thereby illustrated that the Nonmetallocene part is after the chemical processing agent reaction in is combined in load type non-metallocene catalyst provided by the present invention, formed the Nonmetallocene title complex component with catalysis in olefine polymerization activity, it has the effect of the molecular weight distribution of narrowing, and therefore can come the molecular weight distribution of telomerized polymer by regulating the relative proportioning with the complex carrier chemical processing agent of Nonmetallocene part.

Sequence number 1 and 2 test-results data adopt load type non-metallocene catalyst provided by the invention as can be known in the contrast table 1, show significant comonomer effect, and namely under equal relatively condition, the copolymerization activity is higher than the homopolymerization activity.

Test-results data by sequence number 1 in the contrast table 1 and sequence number 12 adopt porous support provided by the present invention to handle the catalyst activity and the polymer stacks density that obtain through chemical processing agent and are higher than porous support without the resulting catalyzer of chemical processing agent as can be known.And the former resulting molecular weight distribution is wider than the latter, illustrates further thus, and method for preparing catalyst provided by the invention, chemical processing agent have the molecular weight distribution of broadening polymkeric substance and improve the effectiveness of polymer stacks density.

Test-results data by sequence number 1 in the contrast table 1 and sequence number 14 as can be known, the catalyst preparation process route that adopts complex carrier provided by the present invention to be obtained by precipitation agent precipitation, and thus the polymer stacks density that obtains of polymerization to be higher than complex carrier be directly to vacuumize dry and resulting catalyzer by mixed serum.And the former resulting molecular weight distribution is suitable with the latter, explanation thus, method for preparing catalyst provided by the invention, the particle form of telomerized polymer effectively.

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

Claims (28)

1. the preparation method of a load type non-metallocene catalyst may further comprise the steps:

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

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

Described modification carrier, described magnesium compound solution are contacted with the Nonmetallocene part, obtain the step of mixed serum;

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

Make the chemical processing agent and the reaction of described complex carrier that are selected from described IVB family metallic compound, obtain the step of described load type non-metallocene catalyst,

Wherein said solvent is selected from C _6-12Aromatic hydrocarbon, halo C _6-12In aromatic hydrocarbon, ester and the ether one or more.

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

3. according to the described preparation method of claim 2, 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 the polynite.

4. according to the described preparation method of claim 3, it is characterized in that described porous support is silicon-dioxide.

5. according to the described preparation method of 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 the alkyl alkoxy magnesium.

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

7. according to the described preparation method of claim 6, it is characterized in that described magnesium compound is magnesium chloride.

8. according to the described preparation method of claim 1, it is characterized in that described solvent is selected from C _6-12In aromatic hydrocarbon and the tetrahydrofuran (THF) one or more.

9. according to the described preparation method of claim 8, it is characterized in that described solvent is tetrahydrofuran (THF).

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

In above chemical structural formula,

Q is 0 or 1;

D is 0 or 1;

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

-NR ²³R ²⁴,-N (O) R ²⁵R ²⁶, -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, contains seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and the P coordination atom of respectively doing for oneself;

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

→ represent singly-bound or two key;

-represent covalent linkage or ionic linkage;

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

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

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

11., it is characterized in that described Nonmetallocene part is selected from compound (A) with following chemical structural formula and in the compound (B) one or more according to the described preparation method of claim 10:

In above all chemical structural formulas,

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

12., it is characterized in that described Nonmetallocene part is selected to compound (A-4) and compound (B-1) to compound (B-4) one or more of compound (A-1) with following chemical structural formula according to the described preparation method of claim 11:

In above all chemical structural formulas,

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

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

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

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

13. according to each described preparation method of claim 10-12, it is characterized in that,

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

Described nitrogen-containing group is selected from

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

Described phosphorus-containing groups is selected from

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

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

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

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

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

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

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

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

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

Described group T ditto defines.

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

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

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

17. according to the described preparation method of claim 16, it is characterized in that, be 1 in the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene part: 0.0008-0.2, the ratio of described magnesium compound and described solvent is 1mol: 150～300ml, be 1 in the described magnesium compound of magnesium compound solid and the mass ratio of described porous support: 0.5-10, the volume ratio of described precipitation agent and described solvent is 1: 0.5～2, and is respectively 1 in the described magnesium compound of Mg element independently of one another with mol ratio in the described chemical processing agent of IVB family metallic element: 0.01-0.50.

18. according to the described preparation method of claim 17, it is characterized in that, be 1 in the described magnesium compound of Mg element and the mol ratio of described Nonmetallocene part: 0.001-0.1, the ratio of described magnesium compound and described solvent is 1mol: 200～250ml, be 1 in the described magnesium compound of magnesium compound solid and the mass ratio of described porous support: 1-5, the volume ratio of described precipitation agent and described solvent is 1: 0.8～1.5, and is respectively 1 in the described magnesium compound of Mg element independently of one another with mol ratio in the described chemical processing agent of IVB family metallic element: 0.10-0.30.

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

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

21., it is characterized in that described IVB family metallic compound is selected from TiCl according to the described preparation method of claim 20 ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄And HfBr ₄In one or more.

22., it is characterized in that described IVB family metallic compound is selected from TiCl according to the described preparation method of claim 21 ₄And ZrCl ₄In one or more.

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

24. according to the described preparation method of claim 23, it is characterized in that described precipitation agent is selected from pentane, hexane, heptane, octane, nonane, decane, hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane, methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three n-butyl bromide, chlorocyclopentane, chlorocyclohexane, the chloro suberane, the chloro cyclooctane, the chloro cyclononane, the chloro cyclodecane, bromocyclopentane, bromocyclohexane, the bromo suberane, the bromo cyclooctane, in bromo cyclononane and the bromo cyclodecane one or more.

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

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

27. a load type non-metallocene catalyst, it is by making according to each described preparation method of claim 1-26.

28. alkene homopolymerization/copolymerization process, it is characterized in that, being Primary Catalysts according to the described load type non-metallocene catalyst of claim 27, be promotor to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more, make alkene homopolymerization or copolymerization.