CN103304706B

CN103304706B - Load type non-metallocene catalyst, its preparation method and application thereof

Info

Publication number: CN103304706B
Application number: CN201210063935.5A
Authority: CN
Inventors: 李传峰; 任鸿平; 郭峰; 阚林; 柏基业; 马忠林; 陈韶辉; 王亚明; 杨爱武
Original assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Current assignee: China Petroleum and Chemical Corp; Sinopec Yangzi Petrochemical Co Ltd
Priority date: 2012-03-06
Filing date: 2012-03-06
Publication date: 2015-12-16
Anticipated expiration: 2032-03-06
Also published as: CN103304706A

Abstract

The present invention relates to a kind of load type non-metallocene catalyst and preparation method thereof.Described load type non-metallocene catalyst has the features such as preparation is simple, Nonmetallocene component concentration is controlled, copolymerization effect is remarkable.The invention still further relates to the application of described load type non-metallocene catalyst in alkene homopolymerization/copolymerization.Described application and prior art have that catalysis in olefine polymerization activity is high, polymer stacks density is high, particle diameter is little and the feature be evenly distributed on year-on-year basis.

Description

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

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

Technical field

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

Background technology

The non-metallocene catalyst that middle and later periods nineteen nineties occurs, after the non cyclopentadienyl catalyst time appears at metallocene catalyst, be therefore otherwise known as " after luxuriant " olefin polymerization catalysis.It has the feature similar to metallocene catalyst, can customize polymkeric substance as required, and cost is lower.The central atom of non-metallocene catalyst includes nearly all transition metal, reaches, even exceed metallocene catalyst at some aspect of performance, becomes the olefin polymerization catalysis of new generation after Ziegler-Natta and metallocene catalyst.According to the difference of the central atom of Primary Catalysts, non-metallocene (IIIB race, IVB race, VB race, group vib, VIIB race) catalyzer and non-luxuriant rear transition metal (VIII) catalyzer can be divided into again further.The excellent property of the polyolefin products manufactured by such catalyzer, and low cost of manufacture.Non-metallocene catalyst ligating atom is oxygen, nitrogen, sulphur and phosphorus, not containing cyclopentadienyl group or its deriveding group, as indenyl and fluorenyl etc., it is characterized in that central ion has stronger Electron Affinities, and there is cis alkyl or halogen metal division center, easily carry out alkene to insert and σ-key transfer, the easy alkylation of central metal, is conducive to the generation at cation activity center; The title complex formed has the geometric configuration of restriction, and stereoselectivity, electronegativity and chirality controllability, in addition, the metal-carbon key formed easily polarizes, and is more conducive to polymerization and the copolymerization of alkene.Therefore, even if the olefin polymer of higher molecular weight also can be obtained under higher polymeric reaction temperature.

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

Patent ZL01126323.7, ZL02151294.9ZL02110844.7 and WO03/010207 disclose a kind of alkene homopolymerization/copolymerization catalyzer or catalyst system, there is alkene homopolymerization/copolymerization performance widely, but the catalyzer disclosed in this patent or catalyst system in olefinic polymerization time need higher promotor consumption, suitable olefin polymerizating activity could be obtained, and it is short to there is active duration in polymerization process, polymkeric substance glues the phenomenons such as still.

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

For patent ZL01126323.7, non-metallocene catalyst disclosed in ZL02151294.9ZL02110844.7 and WO03/010207, patent CN1539855A, CN1539856A, CN1789291A, CN1789292A, CN1789290A, WO/2006/063501, ZL200510119401.x etc. provide various ways and carry out load to obtain load type non-metallocene catalyst, but these patents all relate to and the Nonmetallocene organic compound containing transition metal (or are called non-metallocene catalyst, or Nonmetallocene title complex) be carried on the carrier after process, non-metallocene catalyst charge capacity is lower, it is combined not bery tight with carrier.。

Load type non-metallocene catalyst patent disclosed in patent 200710162667.1,200710162676.0,200910210987.9 and 200910210991.5 provides containing porous oxide, and single take magnesium compound as the Catalysts and its preparation method of carrier.Owing to not having adding of porous oxide carrier, the catalytic performance of load type non-metallocene catalyst obtains and fully plays, and polymerization activity is higher.But this kind of catalyzer adopts the method for vacuum-drying or solvent deposition in carrier moulding process, be difficult to the moulding process and the particle form that control carrier, the therefore more difficult control of the form of polymkeric substance.

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

Patent CN200610026765.8 discloses a class single active center Ziegler-Natta olefin polymerizing catalyst.This catalyzer is using the salicylaldehyde derivatives of the salicylic aldehyde containing coordinating group or replacement as electron donor, by adding through pretreated carrier (as silica gel) in magnesium compound (as magnesium chloride)/tetrahydrofuran solution, metallic compound (as titanium tetrachloride) and this electron donor, obtain after process.Because have employed the skeleton of in type porous support as complex carrier in catalyst preparation process, the form of catalyzer is easier to control, and the form of polymkeric substance also makes moderate progress.

The magnesium halide generated in chemical reaction process also can prepare the olefin polymerization catalysis of load as carrier, and can regulate the formation speed of magnesium halide by controlling chemical reaction process, realizes the morphology Control to magnesium halide carrier with this.And research shows that the magnesium halide generated by Grignard reagent and halide reaction has higher specific surface, unordered crystalline structure (EurPolymJ, 2000,19:19), is suitable for preparing loaded catalyst.

Japanese Patent JP1054005A, JP1054006A and JP63186706A provide the method preparing high activity olefin polymerization catalyst, it makes Grignard reagent MgRX (R is alkyl, X is halogen) obtain magnesium compound carrier with halohydrocarbons reaction, then magnesium halide carrier load halogenated titanium makes loaded catalyst, and the activity of this catalyst olefinic polymerization is higher.

Japanese Patent JP1081803A provides a kind of method preparing olefin polymerization catalysis, it makes Grignard reagent MgRX (R is alkyl, X is halogen) react generate magnesium halide carrier with halogenated compound (as aluminum chloride), then magnesium halide carrier load halogenated titanium makes loaded catalyst.

Japanese Patent JP6192329A provides a kind of method preparing olefin polymerization catalysis, it makes Grignard reagent MgRX (R is alkyl, X is halogen) generate magnesium halide carrier with halohydrocarbons reaction, then carrier and halogenated titanium are obtained by reacting loaded catalyst.The carrier that the method obtains has narrow size distribution, and the catalyzer of preparation has good mobility.

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

Summary of the invention

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

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

Present invention relates in general to a kind of preparation method of load type non-metallocene catalyst, comprise the following steps: make optionally to react with halogenating agent through the porous support of thermal activation treatment and/or the optional chemical processing agent process through being selected from IVB race metallic compound, Grignard reagent, the step of acquisition complex carrier; The chemical processing agent and the described complex carrier that make to be selected from IVB race metallic compound react, and obtain the step of modifying complex carrier; Nonmetallocene title complex is contacted in the presence of the solvent with described modification complex carrier, obtains the step of mixed serum; With mixed serum described in convection drying, obtain the step of described load type non-metallocene catalyst, wherein said preparation method is optionally also included in and makes before described chemical processing agent and described complex carrier react, by the step helping complex carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

This preparation method comprises the first following embodiment and the second embodiment.

First embodiment: a kind of preparation method of load type non-metallocene catalyst, comprises the following steps: the optional porous support through thermal activation treatment, Grignard reagent and halogenating agent are reacted, obtains the step of complex carrier; The chemical processing agent and the described complex carrier that make to be selected from IVB race metallic compound react, and obtain the step of modifying complex carrier; Nonmetallocene title complex is contacted in the presence of the solvent with described modification complex carrier, obtains the step of mixed serum; With mixed serum described in convection drying, obtain the step of described load type non-metallocene catalyst.

Second embodiment: a kind of preparation method of load type non-metallocene catalyst, comprises the following steps: the first chemical processing agent being selected from IVB race metallic compound is reacted with the porous support optionally through thermal activation treatment, obtains the step of modifying porous support; Described modification porous support, Grignard reagent and halogenating agent are reacted, obtains the step of complex carrier; The second chemical processing agent and the described complex carrier that make to be selected from described IVB race metallic compound react, and obtain the step of modifying complex carrier; Nonmetallocene title complex is contacted in the presence of the solvent with described modification complex carrier, obtains the step of mixed serum; With mixed serum described in convection drying, obtain the step of described load type non-metallocene catalyst.

According to the first embodiment, the present invention relates to the content of following aspect:

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

The optional porous support through thermal activation treatment, Grignard reagent and halogenating agent are reacted, obtains the step of complex carrier;

The chemical processing agent and the described complex carrier that make to be selected from IVB race metallic compound react, and obtain the step of modifying complex carrier;

Nonmetallocene title complex is contacted in the presence of the solvent with described modification complex carrier, obtains the step of mixed serum; With

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

2. according to the preparation method described in any preceding aspect, it is characterized in that, described halogenating agent is selected from halo C _1-30one or more in hydrocarbon, are preferably selected from chloro C _1-30hydrocarbon and bromo C _1-30one or more in hydrocarbon, wherein said C _1-30hydrocarbon is C _1-30alkane, C _2-30alkene, C _6-30aromatic hydrocarbons, C _7-30aralkyl hydrocarbon or C _7-30alkane aromatic hydrocarbons, described halogenating agent be preferably selected from monobromethane, monochloroethane, monobromethane, 1-chloro-butane, 1-chloro-hexane, chlorobenzene, bromobenzene and benzyl chloride one or more.

3. according to the preparation method described in any preceding aspect, it is characterized in that, it is one or more in the dialkyl magnesium of (R) (R ') Mg that described Grignard reagent is selected from alkyl magnesium halide that general formula is RMgX and general formula, wherein radicals R and R ' are same to each other or different to each other, and are C independently of one another ₁-C ₃₀alkyl, preferred C ₁-C ₃₀alkyl, C ₂-C ₃₀thiazolinyl, C ₆-C ₃₀aryl, C ₇-C ₃₀alkaryl or C ₇-C ₃₀aralkyl, further preferable methyl, ethyl, isobutyl-, iso-octyl, cyclohexyl, phenyl or benzyl, most preferable or ethyl, X is halogen, preferred chlorine or bromine, described Grignard reagent be preferably selected from methylmagnesium-chloride, ethylmagnesium chloride, phenyl-magnesium-chloride, benzylmagnesium chloride, dimethyl magnesium, magnesium ethide and diphenyl magnesium one or more.

4. according to the preparation method described in any preceding aspect, it is characterized in that, described solvent is selected from C _6-12aromatic hydrocarbon, halo C _6-12aromatic hydrocarbon, halo C _1-10one or more in alkane, ester and ether, be preferably selected from toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and tetrahydrofuran (THF) one or more, more preferably C _6-12one or more in aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).

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

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

with

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

with

In chemical structural formulas all above,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

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

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

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

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

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

D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C ₁-C ₃₀alkyl, sulfuryl, sulfoxide group, -N (O) R ²⁵r ²⁶, or-P (O) R ³²(OR ³³), wherein N, O, S, Se and P are coordination atom separately;

E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are coordination atom separately;

F is selected from nitrogen-atoms, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;

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

Y is selected from Sauerstoffatom, nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group or phosphorus-containing groups, wherein N, O, S, Se and P are coordination atom separately;

Z is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group, wherein N, O, S, Se and P are coordination atom separately;

→ represent singly-bound or double bond;

-represent covalent linkage or ionic linkage;

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

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

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

Described safing function groups be selected from halogens, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group, containing tin group, C ₁-C ₁₀ester group or nitro,

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

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

6., according to the preparation method described in any preceding aspect, it is characterized in that,

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

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

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

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

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

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

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

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

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

The C of described replacement ₁-C ₃₀alkyl is selected from one or more described halogen and/or described C ₁-C ₃₀the described C of alkyl alternatively base ₁-C ₃₀alkyl;

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

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

Described silicon-containing group is selected from-SiR ⁴²r ⁴³r ⁴⁴or-T-SiR ⁴⁵;

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

The described tin group that contains is selected from-SnR ⁵⁰r ⁵¹r ⁵²,-T-SnR ⁵³or-T-Sn (O) R ⁵⁴,

Described Ar represents C ₆-C ₃₀aryl, and

Described 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

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

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

Described group T defines with any preceding aspect.

7. according to the preparation method described in any preceding aspect, it is characterized in that, the mol ratio of described Grignard reagent and described halogenating agent is 1: 1-100, preferably 1: 1-10, more preferably 1: 1-5, in the mol ratio of the described Grignard reagent of Mg element and described Nonmetallocene title complex for 1: 0.0001-1, preferably 1: 0.0002-0.4, more preferably 1: 0.0008-0.2, the amount ratio of described Grignard reagent and described porous support is 1mol: 10-2000g, preferred 1mol: 50-1000g, more preferably 1mol: 100-500g, and in the described Grignard reagent of Mg element with the mol ratio of the described chemical processing agent of IVB race elemental metal for 1: 0.01-1, preferably 1: 0.01-0.50, more preferably 1: 0.05-0.30.

8. according to the preparation method described in any preceding aspect, it is characterized in that, described IVB race metallic compound be selected from IVB race metal halide, IVB race metal alkyl compound, IVB race metal alkoxide, IVB race metal alkyl halides and IVB race metal alkoxide halogenide one or more, be preferably selected from IVB race metal halide one or more, be more preferably selected from TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄and HfBr ₄in one or more, be most preferably selected from TiCl ₄and ZrCl ₄in one or more.

9. according to the preparation method described in any preceding aspect, it is characterized in that, described porous support is selected from olefin homo or multipolymer, polyvinyl alcohol or its multipolymer, cyclodextrin, polyester or copolyesters, polymeric amide or copolyamide, ryuron or multipolymer, Voncoat R 3310 or multipolymer, methacrylate homopolymer or multipolymer, styrene homopolymers or multipolymer, the partial cross-linked form of these homopolymer or multipolymer, periodic table of elements IIA, IIIA, the refractory oxide of IVA or IVB race metal or infusibility composite oxides, clay, molecular sieve, mica, polynite, one or more in wilkinite and diatomite, be preferably selected from partial cross-linked styrene polymer, silicon-dioxide, aluminum oxide, magnesium oxide, oxidation sial, oxidation magnalium, titanium dioxide, one or more in molecular sieve and polynite, more preferably silicon-dioxide is selected from.

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

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

12., according to the preparation method described in any preceding aspect, is characterized in that, in the described magnesium compound of Mg element with to help the mol ratio of chemical processing agent for 1: 0-1.0 described in Al element, preferably 1: 0-0.5, more preferably 1: 0.1-0.5.

13. 1 kinds of load type non-metallocene catalysts, it manufactures by according to the preparation method described in any preceding aspect.

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

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

Load type non-metallocene catalyst is manufactured according to the preparation method described in any preceding aspect, and

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

According to the second embodiment, the present invention relates to the content of following aspect:

The first chemical processing agent being selected from IVB race metallic compound is reacted with the porous support optionally through thermal activation treatment, obtains the step of modifying porous support;

Described modification porous support, Grignard reagent and halogenating agent are reacted, obtains the step of complex carrier;

The second chemical processing agent and the described complex carrier that make to be selected from described IVB race metallic compound react, and obtain the step of modifying complex carrier;

In chemical structural formulas all above,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

→ represent singly-bound or double bond;

-represent covalent linkage or ionic linkage;

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

with

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

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

Described Ar represents C ₆-C ₃₀aryl, and

Described group T defines with any preceding aspect.

7. according to the preparation method described in any preceding aspect, it is characterized in that, the mol ratio of described Grignard reagent and described halogenating agent is 1: 1-100, preferably 1: 1-10, more preferably 1: 1-5, in the mol ratio of the described Grignard reagent of Mg element and described Nonmetallocene title complex for 1: 0.0001-1, preferably 1: 0.0002-0.4, more preferably 1: 0.0008-0.2, the amount ratio of described Grignard reagent and described porous support is 1mol: 10-2000g, preferred 1mol: 50-1000g, more preferably 1mol: 100-500g, in the described Grignard reagent of Mg element with the mol ratio of described first chemical processing agent of IVB race elemental metal for 1: 0.01-1, preferably 1: 0.01-0.50, more preferably 1: 0.05-0.30, and in the described Grignard reagent of Mg element with the mol ratio of described second chemical processing agent of IVB race elemental metal for 1: 0.01-1, preferably 1: 0.01-0.50, more preferably 1: 0.05-0.30.

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

Technique effect

According to the first embodiment, preparation method's technique simple possible of load type non-metallocene catalyst of the present invention, and also the charge capacity of Nonmetallocene title complex is adjustable, can give full play to the performance that its catalysis in olefine polymerization obtains polyolefin product.

According to the first embodiment, adopt method for preparing catalyst provided by the invention, because catalyzer is prepared by chemical processing agent process and load non-metallocene metal complexes two steps, in catalyzer the constituent content of active metal and the molar ratio of regular activated metal and Nonmetallocene title complex controlled, thus effectively control catalyst activity and polymer performance.

According to the first embodiment, method for preparing catalyst provided by the invention, in the hole that magnesium compound and Nonmetallocene part can be made to be attached to porous support uniformly and outside surface, the supported catalyst of preparation has good accumulation form, can prepare the polymkeric substance that particle form is better, bulk density is higher; Nonmetallocene title complex distributes more even in the carrier simultaneously, is more conducive to the performance of Nonmetallocene title complex performance.

According to the second embodiment, preparation method's technique simple possible of load type non-metallocene catalyst of the present invention, and also the charge capacity of Nonmetallocene part and title complex is adjustable, can give full play to the performance that its catalysis in olefine polymerization obtains polyolefin product.

According to the second embodiment, adopt method for preparing catalyst provided by the invention, because catalyzer is prepared by chemical processing agent process and load non-metallocene metal ligand two steps, in catalyzer the constituent content of active metal and the molar ratio of regular activated metal and Nonmetallocene title complex controlled, thus effectively control catalyst activity and polymer performance.

According to the second embodiment, method for preparing catalyst provided by the invention, in the hole that magnesium compound and Nonmetallocene part can be made to be attached to porous support uniformly and outside surface, the supported catalyst of preparation has good accumulation form, can prepare the polymkeric substance that particle form is better, bulk density is higher; Nonmetallocene title complex distributes more even in the carrier simultaneously, is more conducive to the performance of Nonmetallocene title complex performance.

According to the second embodiment, the preparation method of catalyzer provided by the invention, owing to using chemical processing agent to carry out surface treatment to porous support, decrease the impact of surface group on catalyst activity of porous support, the activity of catalyzed polymerization is higher.

Embodiment

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

Below first embodiment of the invention is described.

In the context of the present invention, unless otherwise defined explicitly, or this implication is beyond the understanding scope of those skilled in the art, hydrocarbon more than 3 carbon atoms or hydrocarbon derivative group (such as propyl group, propoxy-, butyl, butane, butylene, butenyl, hexane etc.) not titled with all have time prefix " just " with titled with implication identical time prefix " just ".Such as, propyl group is generally understood as n-propyl, and butyl is generally understood as normal-butyl.

The present invention relates to a kind of preparation method of load type non-metallocene catalyst, comprise the following steps: the optional porous support through thermal activation treatment, Grignard reagent and halogenating agent are reacted, obtains the step of complex carrier; The chemical processing agent and the described complex carrier that make to be selected from IVB race metallic compound react, and obtain the step of modifying complex carrier; Nonmetallocene title complex is contacted in the presence of the solvent with described modification complex carrier, obtains the step of mixed serum; With mixed serum described in convection drying, obtain the step of described load type non-metallocene catalyst.

According to the present invention, the optional porous support through thermal activation treatment, Grignard reagent and halogenating agent are reacted, obtains complex carrier.

Below described Grignard reagent is specifically described.

According to the present invention, as described Grignard reagent, such as can enumerate and be selected from least one that alkyl magnesium halide that general formula is RMgX and general formula are the dialkyl magnesium of (R) (R ') Mg.

In aforementioned formula, radicals R is same to each other or different to each other with R ' (preferably identical), is selected from C independently of one another ₁-C ₃₀alkyl, such as C ₁-C ₃₀alkyl (straight chain, side chain or ring-type), C ₂-C ₃₀thiazolinyl (straight chain, side chain or ring-type), C ₆-C ₃₀aryl, C ₇-C ₃₀alkaryl or C ₇-C ₃₀aralkyl, wherein preferable methyl, ethyl, isobutyl-, iso-octyl, cyclohexyl, phenyl and benzyl, most preferable and ethyl.X is selected from halogen, preferred chlorine and bromine.

As described alkyl magnesium halide, preferable methyl magnesium chloride, ethylmagnesium chloride, propyl group magnesium chloride, n-butylmagnesium chloride magnesium, isobutyl-magnesium chloride, n-hexyl magnesium chloride, isohexyl magnesium chloride, phenyl-magnesium-chloride, benzylmagnesium chloride, methyl-magnesium-bromide, ethylmagnesium bromide, propyl group magnesium bromide, normal-butyl magnesium bromide, selenium alkynide, n-hexyl magnesium bromide, isohexyl magnesium bromide, phenyl-magnesium-bromide and Benzylphosphonium Bromide magnesium, further preferable methyl magnesium chloride, ethylmagnesium chloride, phenyl-magnesium-chloride and benzylmagnesium chloride.

These alkyl magnesium halides can be used alone one, or use multiple with arbitrary ratio combination.

As described dialkyl magnesium, dimethyl magnesium (Mg (CH such as can be enumerated ₃) ₂), magnesium ethide (Mg (CH ₃cH ₂) ₂), dipropyl magnesium (Mg (C ₃h ₇) ₂), diisobutyl magnesium (Mg (i-C ₄h ₉) ₂), di-n-butyl magnesium (Mg (C ₄h ₉) ₂), diisoamyl magnesium (Mg (i-C ₅h ₁₁) ₂), two n-pentyl magnesium (Mg (C ₅h ₁₁) ₂), dihexyl magnesium (Mg (C ₆h ₁₃) ₂), two isohexyl magnesium (Mg (i-C ₆h ₁₃) ₂), methylethyl magnesium (Mg (CH ₃cH ₂) (CH ₃)), diphenyl magnesium (Mg (C ₆h ₅) ₂) and dibenzyl magnesium (Mg [CH ₂(C ₆h ₅)] ₂) etc., wherein preferred dimethyl magnesium, magnesium ethide, diisobutyl magnesium, dicyclohexyl magnesium, diphenyl magnesium and dibenzyl magnesium, most preferably dimethyl magnesium, diphenyl magnesium and magnesium ethide.

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

According to the present invention, as described Grignard reagent, only can adopt described alkyl magnesium halide, also only can adopt described dialkyl magnesium, but also can adopt any mixture of described alkyl magnesium halide and described dialkyl magnesium.And to the ratio of component each in this mixture, there is no particular limitation, can select arbitrarily as required.

Grignard reagent involved in the present invention can manufacture according to the method for well known to a person skilled in the art, also can directly use commercially available product, there is no particular limitation.

According to the present invention, halogenating agent is selected from halo C _1-30at least one in hydrocarbon, preferred chloro and/or bromo C _1-30at least one in hydrocarbon.According to the present invention one preferred embodiment, described C _1-30hydrocarbon is selected from C _1-30alkane, C _2-30alkene, C _6-30aromatic hydrocarbons, C _7-30aralkyl hydrocarbon and C _7-30alkane aromatic hydrocarbons.It is further preferred that described halogenating agent is selected from monobromethane, monochloroethane, monobromethane, 1-chloro-butane, 1-chloro-hexane, chlorobenzene, bromobenzene and benzyl chloride.

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

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

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

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

According to an embodiment of the invention, before use thermal activation treatment is carried out to described Porous-Organic solid.This thermal activation treatment can be carried out according to common mode, such as carries out heat treated to described Porous-Organic solid at reduced pressure conditions or under inert atmosphere.Inert atmosphere mentioned here to refer in gas only containing extremely trace or containing can with the component of described Porous-Organic solid reaction.As described inert atmosphere, nitrogen or rare gas atmosphere such as can be enumerated, preferred nitrogen atmosphere.Due to the poor heat resistance of Porous-Organic solid, therefore this thermal activation process is premised on the structure not destroying described Porous-Organic solid itself and essentially consist.Usually, the temperature of this thermal activation is 50 ~ 400 DEG C, preferably 100 ~ 250 DEG C, and the thermal activation time is 1 ~ 24h, preferably 2 ~ 12h.After thermal activation treatment, described Porous-Organic solid needs malleation under an inert atmosphere to save backup.

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

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

According to the present invention, suitable silicon-dioxide can be manufactured by ordinary method, or can be the commerical prod can bought arbitrarily, such as can enumerate Grace955, Grace948, GraceSP9-351, GraceSP9-485, GraceSP9-10046, DavsionSyloid245 and Aerosil812 of Grace company, ES70, ES70X, ES70Y, ES70W, ES757, EP10X and EP11 of Ineos company, and CS-2133 and MS-3040 of Pq Corp..

According to the present invention's preferred embodiment, preferably on the surface of described inorganic porous solids with hydroxyl isoreactivity functional group.

According to the present invention, in one embodiment, before use thermal activation treatment is carried out to described inorganic porous solids.This thermal activation treatment can be carried out according to common mode, such as carries out heat treated to described inorganic porous solids at reduced pressure conditions or under inert atmosphere.Inert atmosphere mentioned here refers in gas and only contains extremely micro-or do not contain the component can reacted with described inorganic porous solids.As described inert atmosphere, nitrogen or rare gas atmosphere such as can be enumerated, preferred nitrogen atmosphere.Usually, the temperature of this thermal activation is 200-800 DEG C, preferably 400 ~ 700 DEG C, most preferably 400 ~ 650 DEG C, and heat-up time is such as 0.5 ~ 24h, preferably 2 ~ 12h, most preferably 4 ~ 8h.After thermal activation treatment, described inorganic porous solids needs malleation under an inert atmosphere to save backup.

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

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

According to the present invention, in order to obtain described complex carrier, generally make describedly optionally to carry out under the existence of solvent (hereinafter sometimes referred to dissolving Grignard reagent solvent or the first solvent) through the reaction of the porous support of thermal activation treatment, described Grignard reagent and described halogenating agent.To now used solvent, there is no particular limitation, as long as it can dissolve this Grignard reagent and this halogenating agent and with them, chemical reaction not occur.

As described solvent, such as C can be enumerated _2-16chain ether (preferred C _4-12chain ether) and C _2-16cyclic ethers (preferred C _4-12cyclic ethers) in one or more, wherein preferably ether, n-butyl ether, tetrahydrofuran (THF) and Isosorbide-5-Nitrae-dioxane or its combine arbitrarily.

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

According to the present invention, to the consumption of described dissolving Grignard reagent solvent, there is no particular limitation, can suitably select as required, as long as it can realize aforesaid reaction.Generally speaking, as the overall consumption of described dissolving Grignard reagent solvent in the step of this acquisition complex carrier (such as comprising the consumption during solution of preparation as follows except grignard reagent solution), such as can be set as making described Grignard reagent (solid) reach 1mol: 200 ~ 3000ml with the ratio of described solvent, preferred 1mol: 500 ~ 2000ml, more preferably 1mol: 500 ~ 1000ml, but be obviously not limited to this, those skilled in the art can carry out suitable adjustment completely as required.

According to the present invention, to reactive mode under solvent (the first solvent) exists of the optional porous support through thermal activation treatment, Grignard reagent and halogenating agent, there is no particular limitation.Such as can enumerate, (now respective used dissolving Grignard reagent solvent can be identical for the solution (as required) of the solution first utilizing aforementioned dissolving Grignard reagent solvent to prepare described Grignard reagent respectively and described halogenating agent, also can be different), then in described grignard reagent solution successively or be metered into simultaneously or drip described optionally through the porous support of thermal activation treatment and described halogenating agent or halogenating agent solution, or it is described optionally through the porous support of thermal activation treatment to measure mixing simultaneously or successively, the mode of described grignard reagent solution and described halogenating agent solution, or, optionally measure interpolation (preferably dripping) to the mode etc. in described dissolving Grignard reagent solvent through the porous support of thermal activation treatment, described Grignard reagent and described halogenating agent by described simultaneously or successively, but be not limited to this.Wherein, preferred elder generation prepares described grignard reagent solution as previously mentioned, then be metered into described optionally through the porous support of thermal activation treatment wherein, obtain mixed serum, then halogenating agent or halogenating agent solution measures are added (preferably dripping) to the mode in described mixed serum.

According to the present invention, in order to manufacture described complex carrier, such as can at normal temperature at the temperature lower than the boiling point of used any solvent, the optional porous support through thermal activation treatment, Grignard reagent and halogenating agent reaction is in the presence of solvent made to carry out 0.5-48h altogether, preferred 1-24h, optimum 2-8h (if desired by stirring).

After reaction terminates, obtained solid product filtered, wash and drying, obtain described complex carrier thus.Method for described filtration, washing and drying is not particularly limited, this area routine can be used as required to use those.

As required, described washing generally carries out 1 ~ 6 time, preferably 3 ~ 4 times.Wherein, washer solvent preferably uses the solvent same with described dissolving Grignard reagent solvent phase, but also can be different.Described drying can adopt ordinary method to carry out, such as rare gas element desiccating method, boulton process or heating under vacuum desiccating method, preferred rare gas element desiccating method or heating under vacuum desiccating method, most preferably heating under vacuum desiccating method.The temperature range of described drying is generally 30 ~ 160 DEG C, and preferably 60 ~ 130 DEG C, time of drying is generally 2 ~ 24h, but is not limited to this.

Then, the chemical processing agent and the described complex carrier that make to be selected from IVB race metallic compound react, and obtain and modify complex carrier.

Below described chemical processing agent is specifically described.

According to the present invention, using IVB race metallic compound as described chemical processing agent.

As described IVB race metallic compound, such as can enumerate and be selected from IVB race metal halide, IVB race metal alkyl compound, IVB race metal alkoxide, IVB race metal alkyl halides and the halid at least one of IVB race metal alkoxide.

As described IVB race metal halide, described IVB race metal alkyl compound, described IVB race metal alkoxide, described IVB race metal alkyl halides and described IVB race metal alkoxide halogenide, the compound of following formula such as can be enumerated:

M(OR ¹) _mX _nR ² _4-m-n

Wherein:

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

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

M is IVB race metal, such as titanium, zirconium and hafnium etc. in the periodic table of elements;

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, such as methyl, ethyl, propyl group, normal-butyl, isobutyl-etc., R ¹and R ²can be identical, also can be different.

Specifically, as described IVB race metal halide, such as titanium tetrafluoride (TiF can be enumerated 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 IVB race metal alkyl compound, tetramethyl-titanium (Ti (CH such as can be enumerated 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 methyl titanium (Ti (CH ₃) (CH ₃cH ₂) ₃), diethyl-dimethyl titanium (Ti (CH ₃) ₂(CH ₃cH ₂) ₂), trimethylethyl 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 methyl zirconium (Zr (CH ₃) (CH ₃cH ₂) ₃), diethyl-dimethyl zirconium (Zr (CH ₃) ₂(CH ₃cH ₂) ₂), trimethylethyl 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 methyl hafnium (Hf (CH ₃) (CH ₃cH ₂) ₃), diethyl-dimethyl hafnium (Hf (CH ₃) ₂(CH ₃cH ₂) ₂), trimethylethyl 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 IVB race metal alkoxide, tetramethoxy titanium (Ti (OCH such as can be enumerated 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 IVB race metal alkyl halides, trimethyl ammonia chloride titanium (TiCl (CH such as can be enumerated ₃) ₃), triethyl titanium chloride (TiCl (CH ₃cH ₂) ₃), triisobutyl titanium chloride (TiCl (i-C ₄h ₉) ₃), three n-butylmagnesium chloride 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 n-butylmagnesium chloride 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 titanium bromide (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 titanium bromide (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);

Trimethyl ammonia chloride zirconium (ZrCl (CH ₃) ₃), triethyl zirconium chloride (ZrCl (CH ₃cH ₂) ₃), triisobutyl zirconium chloride (ZrCl (i-C ₄h ₉) ₃), three n-butylmagnesium chloride 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 n-butylmagnesium chloride 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 zirconium bromide (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 zirconium bromide (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);

Trimethyl ammonia chloride hafnium (HfCl (CH ₃) ₃), triethyl hafnium chloride (HfCl (CH ₃cH ₂) ₃), triisobutyl hafnium chloride (HfCl (i-C ₄h ₉) ₃), three n-butylmagnesium chloride 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 n-butylmagnesium chloride 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 IVB race metal alkoxide halogenide, trimethoxy titanium chloride (TiCl (OCH such as can be enumerated ₃) ₃), triethoxy titanium chloride (TiCl (OCH ₃cH ₂) ₃), three isobutoxy titanium chloride (TiCl (i-OC ₄h ₉) ₃), three n-Butoxyl titanium-chlorides (TiCl (OC ₄h ₉) ₃), dimethoxy titanium dichloride (TiCl ₂(OCH ₃) ₂), diethoxy titanium dichloride (TiCl ₂(OCH ₃cH ₂) ₂), two isobutoxy titanium dichloride (TiCl ₂(i-OC ₄h ₉) ₂), three n-Butoxyl titanium-chlorides (TiCl (OC ₄h ₉) ₃), methoxytitanium trichloride (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), nbutoxytitanium trichloride (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 IVB race metallic compound, preferred described IVB race metal halide, more preferably TiCl ₄, TiBr ₄, ZrCl ₄, ZrBr ₄, HfCl ₄and HfBr ₄, most preferably TiCl ₄and ZrCl ₄.

These IVB race metallic compounds can be used alone one, or use multiple with arbitrary ratio combination.

When described chemical processing agent is liquid at normal temperatures, can by using described chemical processing agent to the mode of the described chemical processing agent having directly dropping predetermined amount in the reaction object of this chemical processing agent process to be utilized (than complex carrier as the aforementioned).

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

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

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

In addition, to the concentration of described chemical processing agent in its solution, there is no particular limitation, can suitably select as required, as long as it can realize with the described chemical processing agent of predetermined amount to implement described chemical treatment.As previously mentioned, if chemical processing agent is liquid, chemical processing agent directly can be used to carry out described process, but use after also can being modulated into chemical treatment agent solution.

Easily, the volumetric molar concentration of described chemical processing agent in its solution is generally set as 0.01 ~ 1.0mol/L, but is not limited to this.

As carrying out described chemically treated method, such as can enumerate, when chemical processing agent is solid-state (such as zirconium tetrachloride), first the solution of described chemical processing agent is prepared, then in pending reaction object (than complex carrier as the aforementioned), the described solution of (preferably dripping) the described chemical processing agent containing predetermined amount is added, to carry out chemical treatment reaction.When chemical processing agent is liquid (such as titanium tetrachloride), directly the described chemical processing agent of predetermined amount can be added in (preferably dripping) pending reaction object (than complex carrier as the aforementioned), to carry out chemical treatment reaction, or after this chemical processing agent is prepared into solution, the described solution of (preferably dripping) the described chemical processing agent containing predetermined amount is added, to carry out chemical treatment reaction in pending reaction object (than complex carrier as the aforementioned).

Generally speaking, under the temperature of reaction of-30 ~ 60 DEG C (preferably-20 ~ 30 DEG C), make chemical treatment react (if desired by stirring) and carry out 0.5 ~ 24 hour, preferably 1 ~ 8 hour, more preferably 2 ~ 6 hours.

After chemical treatment reaction terminates, by filtering, washing and drying, can obtain through chemically treated product, namely described modification complex carrier.

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

Described drying can adopt ordinary method to carry out, such as rare gas element desiccating method, boulton process or heating under vacuum desiccating method, preferred rare gas element desiccating method or heating under vacuum desiccating method, most preferably heating under vacuum desiccating method.The temperature range of described drying is generally normal temperature to 140 DEG C, and time of drying is generally 2-20 hour, but is not limited to this.

That is, according to the present invention, after the reaction of the described chemical processing agent of use terminates, by aforesaid filtration, washing and drying, obtained process product is separated completely, and then use this process product to carry out next step reaction or process.

According to the present invention, term " Nonmetallocene title complex " is a kind of single centre olefin polymerization catalysis for metallocene catalyst, not containing the cyclopentadienyl or derivatives thereof such as luxuriant ring, fluorenes ring or indenes ring in structure, and the organometallics (therefore described Nonmetallocene title complex is also sometimes referred to as non-metallocene olefin polymerization title complex) of olefinic polymerization catalysis activity can be demonstrated when combining with promotor (than as mentioned below those).This compound comprises the polydentate ligand (preferred tridentate ligand or more tooth part) that central metal atom is combined with coordinate bond with at least one and described central metal atom, and term " Nonmetallocene part " is aforesaid polydentate ligand.

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

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

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

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

with

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

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from periodic table of elements III-th family to XI race atoms metal, preferably IVB race atoms metal, such as can enumerate Ti (IV), Zr (IV), Hf (IV), Cr (III), Fe (III), Ni (II), Pd (II) or Co (II);

E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, containing seleno group, phosphorus-containing groups or cyano group (-CN), wherein N, O, S, Se and P are coordination atom separately;

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

→ represent singly-bound or double bond;

-represent covalent linkage or ionic linkage;

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

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

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

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

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

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

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

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

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

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

(1) complexation process of described group A, D, E, F, Y or Z and described central metal atom M is not disturbed, and

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

In the context of the present invention, described boron-containing group is selected from BF ₄ ^-, (C ₆f ₅) ₄b ^-or (R ⁴⁰bAr ₃) ^-; Describedly be selected from aluminum alkyls, AlPh containing aluminium base group ₄ ^-, AlF ₄ ^-, AlCl ₄ ^-, AlBr ₄ ^-, AlI ₄ ^-or R ⁴¹alAr ₃ ^-; Described silicon-containing group is selected from-SiR ⁴²r ⁴³r ⁴⁴or-T-SiR ⁴⁵; Described germanic group is selected from-GeR ⁴⁶r ⁴⁷r ⁴⁸or-T-GeR ⁴⁹; The described tin group that contains is selected from-SnR ⁵⁰r ⁵¹r ⁵²,-T-SnR ⁵³or-T-Sn (O) R ⁵⁴, wherein Ar represents C ₆-C ₃₀aryl.R ⁴⁰to R ⁵⁴be selected from hydrogen, aforesaid C independently of one another ₁-C ₃₀the C of alkyl, aforesaid replacement ₁-C ₃₀alkyl or aforesaid safing function group, above-mentioned group can be the same or different to each other, and wherein adjacent group can combine togather into key or Cheng Huan.Wherein, the definition of group T is the same, described 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 described R ⁵be selected from lone-pair electron on nitrogen, hydrogen, C ₁-C ₃₀the C of alkyl, replacement ₁-C ₃₀alkyl, oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups; Work as R ⁵for oxy radical, sulfur-containing group, nitrogen-containing group, containing seleno group or phosphorus-containing groups time, R ⁵in N, O, S, P and Se can carry out coordination as coordination atom and described center IVB race atoms metal.

As described Nonmetallocene title complex, such as following compound can be enumerated:

Described Nonmetallocene title complex is preferably selected from following compound:

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

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

These Nonmetallocene title complexs can be used alone one, or use multiple with arbitrary ratio combination.

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

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

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

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

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

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

According to the present invention, when manufacturing described mixed serum, to described second solvent (hereinafter sometimes referred to dissolving Nonmetallocene title complex solvent), there is no particular limitation, as long as it can dissolve described Nonmetallocene title complex.As described second solvent, such as C can be enumerated _6-12aromatic hydrocarbon, halo C _6-12aromatic hydrocarbon, halo C _1-10one or more in alkane, ester and ether.Specifically such as can enumerate toluene, dimethylbenzene, trimethylbenzene, ethylbenzene, diethylbenzene, chlorotoluene, chloro ethylbenzene, bromotoluene, bromo ethylbenzene, methylene dichloride, ethylene dichloride, ethyl acetate and tetrahydrofuran (THF) etc.Wherein, preferred C _6-12aromatic hydrocarbon, methylene dichloride and tetrahydrofuran (THF).

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

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

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

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

According to the present invention's special embodiment, the preparation method of load type non-metallocene catalyst of the present invention is also included in and makes before described chemical processing agent and described complex carrier react, by the step (pre-treatment step) helping complex carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

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

According to the present invention, help chemical processing agent as described, such as can enumerate aikyiaiurnirsoxan beta and aluminum alkyls.

As described aikyiaiurnirsoxan beta, such as can enumerate the linear alumoxanes shown in following general formula (I): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the Cyclic aluminoxane shown in following general formula (II) :-(Al (R)-O-) _n+2-.

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

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

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

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

Al(R) ₃

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

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

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

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

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

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

Through described pre-treatment step, obtain thus through pretreated complex carrier.Then, then carry out reacting with aforementioned same chemical treatment with described chemical processing agent according to aforementioned identical mode, just described complex carrier is replaced with described through pretreated complex carrier.

Namely, by reacting with aforementioned same chemical treatment, make to be selected from the chemical processing agent of described IVB race metallic compound and describedly react to manufacture modification complex carrier through pretreated complex carrier, and manufacturing load type non-metallocene catalyst of the present invention according to mode same before further.

As the method for carrying out described pre-treatment step, such as can enumerate, first the solution of chemical processing agent is helped described in preparing, then help in the pretreated described complex carrier of chemical processing agent described in using to plan to be metered into described in (preferably dripping) and help chemical treatment agent solution (wherein helping chemical processing agent containing described in predetermined amount), or add described complex carrier, forming reactions mixed solution thus to the described chemical treatment agent solution amount of falling into a trap that helps.Now, temperature of reaction is generally-40 ~ 60 DEG C, and preferably-30 ~ 30 DEG C, the reaction times is generally 1 ~ 8h, preferably 2 ~ 6h, most preferably 3 ~ 4h (if desired by stirring).Then, by filtering, washing and optionally drying, from this reaction mixture, pretreatment product is isolated.

Or, according to circumstances, also follow-up reactions steps can be directly used in without this separation with the form of mixed solution.Now, due in described mixed solution containing a certain amount of solvent, so the solvent load that can relate in the described subsequent reactions step of corresponding minimizing.

According to the present invention, described filtration, washing and drying can adopt ordinary method to carry out, wherein washer solvent can adopt with dissolve described in help chemical processing agent time identical solvent used.As required, this washing generally carries out 1 ~ 8 time, preferably 2 ~ 6 times, most preferably 2 ~ 4 times.Described drying can adopt ordinary method to carry out, such as rare gas element desiccating method, boulton process or heating under vacuum desiccating method, preferred rare gas element desiccating method or heating under vacuum desiccating method, most preferably heating under vacuum desiccating method.The temperature range of described drying is generally normal temperature to 140 DEG C, and time of drying is generally 2-20 hour, but is not limited to this.

According to the present invention, as the consumption of described halogenating agent, the mol ratio of described Grignard reagent and described halogenating agent is made to reach 1: 1-100, preferably 1: 1-10, more preferably 1: 1-5.

According to the present invention, as the consumption of described Nonmetallocene title complex, make to reach 1: 0.0001-1 in the mol ratio of the described Grignard reagent (solid) of Mg element and described Nonmetallocene title complex, preferably 1: 0.0002-0.4, more preferably 1: 0.0008-0.2.

According to the present invention, as the consumption of described porous support, make to reach 1mol: 10-2000g, preferred 1mol: 50-1000g in the amount ratio of the described Grignard reagent of Grignard reagent solid and described porous support, more preferably 1mol: 100-500g.

According to the present invention, as the consumption of described chemical processing agent, make in the described Grignard reagent (solid) of Mg element and reach 1: 0.01-1 in the mol ratio of the described chemical processing agent of IVB race metal (such as Ti) element, preferably 1: 0.01-0.50, more preferably 1: 0.05-0.30.

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

Known to those skilled in the art, aforementioned all method stepss are all preferred to carry out under the condition of anhydrous and oxygen-free substantially.Substantially the content that anhydrous and oxygen-free mentioned here refers to water and oxygen in system continues to be less than 100ppm.And load type non-metallocene catalyst of the present invention needs pressure-fired rare gas element (such as nitrogen, argon gas, helium etc.) in confined conditions to save backup under existing after the production usually.

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

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

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

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

Primary Catalysts and promotor can be first add Primary Catalysts to the feed postition in polymerization reaction system, and then add promotor, or first add promotor, and then add Primary Catalysts, or both first contact mixing after add together, or to add respectively simultaneously.Primary Catalysts and promotor are added respectively and fashionablely both can to add successively in same Feed lines, also can add successively in multichannel Feed lines, and both add respectively simultaneously and fashionablely should select multichannel Feed lines.For continous way polyreaction, preferred multichannel Feed lines adds simultaneously continuously, and for intermittence type polymerization reaction, preferably adds together in same Feed lines after both first mixing, or in same Feed lines, first add promotor, and then add Primary Catalysts.

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

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

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

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

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

As described aikyiaiurnirsoxan beta, such as can enumerate the linear alumoxanes shown in following general formula (I-1): (R) (R) Al-(Al (R)-O) _n-O-Al (R) (R), and the Cyclic aluminoxane shown in following general formula (II-1) :-(Al (R)-O-) _n+2-.

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

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

Al(R) ₃

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

As described haloalkyl aluminium, such as the compound shown in following general formula can be enumerated:

Al(R) _nX _3-n

Wherein, radicals R is same to each other or different to each other (preferably identical), and is selected from C independently of one another ₁-C ₈alkyl, preferable methyl, ethyl and isobutyl-, most preferable.Radicals X is halogen, preferred chlorine.N is 1 or 2.

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

Chloromethyl aluminium triethyl (Al (CH ₃) (CH ₃cH ₂) Cl), chloromethyl propyl group aluminium (Al (CH ₃) (C ₃h ₇) Cl), chloromethyl n-butylaluminum (Al (CH ₃) (C ₄h ₉) Cl), chloromethyl aluminium isobutyl (Al (CH ₃) (i-C ₄h ₉) Cl), a chloroethyl propyl group aluminium (Al (CH ₂cH ₃) (C ₃h ₇) Cl), a chloroethyl n-butylaluminum (AlCH ₂cH ₃) (C ₄h ₉) Cl), chloromethyl aluminium isobutyl (AlCH ₂cH ₃) (i-C ₄h ₉) Cl) etc., wherein preferred aluminium diethyl monochloride, ethyl aluminum dichloride, a chlorine di-n-butyl aluminium, dichloro n-butylaluminum, a chloro-di-isobutyl aluminum, dichloro aluminium isobutyl, a chlorine di-n-hexyl aluminium, dichloro n-hexyl aluminium, further preferably chlorodiethyl aluminium, ethyl aluminum dichloride and a chlorine di-n-hexyl aluminium, and most preferably aluminium diethyl monochloride.

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

As described boron fluothane, described boron alkyl and described boron alkyl ammonium salt, directly can use those of this area routine use, not special restriction.

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

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

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

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

These solvent for polymerization can be used alone one, or use multiple with arbitrary ratio combination.

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

In addition, according to the present invention, described alkene homopolymerization/copolymerization method can be carried out having under hydrogen existent condition, also can not have to carry out under hydrogen existent condition.In case of presence, the dividing potential drop of hydrogen can be 0.01% ~ 99% of described polymerization pressure, preferably 0.01% ~ 50%, but be sometimes not limited to this.

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

Embodiment

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

(unit is g/cm to polymer stacks density ³) mensuration carry out with reference to CNS GB1636-79.

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

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

Molecular weight Mw, Mn of polymkeric substance and molecular weight distribution (Mw/Mn) adopt the GPCV2000 type gel chromatography analyser of WATERS company of the U.S. to measure, and with 1,2,4-trichlorobenzene for solvent, temperature during mensuration is 150 DEG C.

The viscosity-average molecular weight of polymkeric substance calculates in accordance with the following methods: according to standard A STMD4020-00, (capillary inner diameter is 0.44mm to adopt high temperature dilution type Ubbelohde viscometer method, thermostatic bath medium is No. 300 silicone oil, dilution solvent is perhydronaphthalene, measuring temperature is 135 DEG C) measure the limiting viscosity of described polymkeric substance, then according to the viscosity-average molecular weight Mv of polymkeric substance described in following formulae discovery.

Mv＝5.37×10 ⁴×[η] ^1.37

Wherein, η is limiting viscosity.

Embodiment 1

Grignard reagent adopts methylmagnesium-chloride (MeMgCl), and dissolve Grignard reagent solvent and adopt tetrahydrofuran (THF), halogenating agent adopts n-propylcarbinyl chloride, porous support adopts silicon-dioxide, i.e. silica gel, model is the ES757 of Ineos company, and Nonmetallocene title complex employing structure is compound, chemical processing agent adopt titanium tetrachloride, second solvent adopt methylene dichloride.

First by silica gel 600 DEG C, continue roasting 4h and thermal activation under nitrogen atmosphere.

Take the silica gel activated, join under normal temperature in grignard reagent solution (containing 0.1mol Grignard reagent) and form homogeneous slurries, be added drop-wise to by halogenating agent under stirring at normal temperature in these homogeneous slurries, time for adding is 30 minutes.After being added dropwise to complete, stir 2 hours under normal temperature.Solid collected by filtration component, solid ingredient hexanes wash 2 times, each hexane consumption 60ml, at 60 DEG C, vacuum-drying obtains complex carrier.

Then in complex carrier, add 60ml hexane, drip chemical processing agent, stirring reaction 4 hours at 60 DEG C with 30 minutes under agitation at normal temperatures, filter, hexanes wash 2 times, each hexane consumption 60ml, under normal temperature, vacuum-drying obtains modifying complex carrier.

Take Nonmetallocene title complex, dissolvedly in the second solvent, make uniform solution, this uniform solution joined in described modification complex carrier under normal temperature, uniform stirring makes mixed serum.Stir 4 hours under normal temperature, under normal temperature, vacuum-drying obtains load type non-metallocene catalyst.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 1000mL, Grignard reagent and halogenating agent mol ratio are 1: 1; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.05; Grignard reagent and chemical processing agent mol ratio are 1: 0.10; The amount ratio of Grignard reagent and porous support is 1mol: 200g; The ratio of Nonmetallocene title complex and the second solvent is 0.05 grams per milliliter.

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

Embodiment 2

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

Grignard reagent adopts ethylmagnesium chloride (EtMgCl), and dissolve Grignard reagent solvent and adopt ether, halogenating agent adopts chloric ethane, and Nonmetallocene title complex adopts porous support changes into 955 type silica gel of Grace company, 400 DEG C, continue roasting 8h and thermal activation under nitrogen atmosphere, chemical processing agent adopts titanium tetrachloride, and the second solvent adopts trichloromethane.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 500mL, Grignard reagent and halogenating agent mol ratio are 1: 2; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.1; Grignard reagent and chemical processing agent mol ratio are 1: 0.20; The amount ratio of Grignard reagent and porous support is 1mol: 100g; The ratio of Nonmetallocene title complex and the second solvent is 0.15 grams per milliliter.

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

Embodiment 3

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

Grignard reagent changes into ethylmagnesium bromide (EtMgBr), and dissolve Grignard reagent solvent and adopt n-butyl ether, Nonmetallocene title complex adopts halogenating agent adopts monobromethane, and chemical processing agent changes into titanium tetrabromide (TiBr ₄), porous support adopts aluminium sesquioxide.By aluminium sesquioxide 700 DEG C, continue roasting 6h under nitrogen atmosphere, the second solvent adopts benzene.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 2000mL; Grignard reagent and halogenating agent mol ratio are 1: 1.5; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.2; Grignard reagent and chemical processing agent mol ratio are 1: 0.30; The amount ratio of Grignard reagent and porous support is 1mol: 500g; The ratio of Nonmetallocene title complex and the second solvent is 0.08 grams per milliliter.

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

Embodiment 4

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

Grignard reagent changes into phenyl-magnesium-chloride (C ₆h ₅mgCl), dissolve Grignard reagent solvent and adopt tetrahydrofuran (THF), Nonmetallocene title complex adopts halogenating agent adopts chlorobenzene, and chemical processing agent adopts tetraethyl-titanium (Ti (CH ₃cH ₂) ₄), porous support adopts polynite.By polynite 400 DEG C, continue roasting 8h under nitrogen atmosphere, the second solvent adopts toluene.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 500mL; Grignard reagent and halogenating agent mol ratio are 1: 1.1; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.04; Grignard reagent and chemical processing agent mol ratio are 1: 0.05; The amount ratio of Grignard reagent and porous support is 1mol: 50g; The ratio of Nonmetallocene title complex and the second solvent is 0.30 grams per milliliter.

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

Embodiment 5

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

Grignard reagent changes into methyl-magnesium-bromide (CH ₃mgBr), dissolve Grignard reagent solvent and adopt Isosorbide-5-Nitrae-dioxane, Nonmetallocene title complex adopts halogenating agent adopts bromocyclohexane, and chemical processing agent adopts tetra-n-butyl titanium (Ti (C ₄h ₉) ₄), porous support adopts the polystyrene of partial cross-linked (degree of crosslinking is 30%).By this polystyrene 100 DEG C, continue under nitrogen atmosphere to dry 12h, the second solvent adopts ethylbenzene.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 2500mL; Grignard reagent and halogenating agent mol ratio are 1: 1.5; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.30; Grignard reagent and chemical processing agent mol ratio are 1: 0.50; The amount ratio of Grignard reagent and porous support is 1mol: 2000g; The ratio of Nonmetallocene title complex and the second solvent is 0.10 grams per milliliter.

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

Embodiment 6

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

Grignard reagent changes into benzylmagnesium chloride (Mg (PhCH ₂) Cl), dissolve Grignard reagent solvent and adopt ethyl n-propyl ether, Nonmetallocene title complex adopts halogenating agent adopts Benzyl Chloride, and chemical processing agent adopts tetraethyl-zirconium (Zr (CH ₃cH ₂) ₄), porous support adopts diatomite, by diatomite 500 DEG C, continue roasting 8h under nitrogen atmosphere.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 667mL; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.10; Grignard reagent and chemical processing agent mol ratio are 1: 0.10; The amount ratio of Grignard reagent and porous support is 1mol: 200g.

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

Embodiment 7

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

Grignard reagent changes into cyclohexyl magnesium chloride (Mg (C ₆h ₁₁) Cl), dissolve Grignard reagent solvent and adopt ether, Nonmetallocene title complex adopts halogenating agent adopts chlorocyclohexane, and chemical processing agent adopts purity titanium tetraethoxide (Ti (OCH ₃cH ₂) ₄).

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

Embodiment 8

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

Grignard reagent changes into magnesium ethide (Mg (C ₂h ₅) ₂), dissolve Grignard reagent solvent and adopt ether, Nonmetallocene title complex adopts halogenating agent adopts chloro normal hexane, and chemical processing agent adopts isobutyl-titanous chloride (Ti (i-C ₄h ₉) Cl ₃).

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

Embodiment 9

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

Grignard reagent changes into dihexyl magnesium (Mg (C ₆h ₁₃) ₂), dissolve Grignard reagent solvent and adopt ether, chemical processing agent changes into three isobutoxy titanium chloride (TiCl (i-OC ₄h ₉) ₃).

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

Embodiment 10

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

Grignard reagent changes into ethyl normal-butyl magnesium (Mg (C ₄h ₉) (C ₂h ₅)), dissolve Grignard reagent solvent and adopt ether, chemical processing agent changes into dimethoxy zirconium dichloride (ZrCl ₂(OCH ₃) ₂).

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

Embodiment 11

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

60ml hexane is added to obtained complex carrier, dripped with 30 minutes under agitation at normal temperatures and help chemical processing agent triethyl aluminum (0.88mol/L, hexane solution), stirring reaction 4 hours at 60 DEG C, filter, hexanes wash 2 times, each hexane consumption 60ml, under normal temperature, vacuum-drying obtains pretreated complex carrier.

Replace described complex carrier with this pretreated complex carrier, prepare load type non-metallocene catalyst similarly to Example 1.

Wherein proportioning is, in the described Grignard reagent of Mg element and to help the mol ratio of chemical processing agent for 1: 0.3 described in Al element.

Load type non-metallocene catalyst is designated as CAT-11.

Embodiment 12

Substantially the same manner as Example 11, but have following change:

Triethyl aluminum (0.88mol/L, hexane solution) is changed into methylaluminoxane (10wt%, toluene solution).

Wherein proportioning is, in the described Grignard reagent of Mg element and to help the mol ratio of chemical processing agent for 1: 0.2 described in Al element.

Load type non-metallocene catalyst is designated as CAT-12.

Comparative example A

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

Grignard reagent and chemical processing agent mol ratio are 1: 0.20.

Catalyzer is designated as CAT-A.

Comparative example B

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

Grignard reagent and Nonmetallocene title complex mol ratio change into 1: 0.10;

Catalyzer is designated as CAT-B.

Comparative example C

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

Grignard reagent and Nonmetallocene title complex mol ratio change into 1: 0.03;

Catalyzer is designated as CAT-C.

Comparative example D

The Nonmetallocene title complex of same structure, identical chemical processing agent and identical porous support is adopted with embodiment 1.

Take 0.1mol Magnesium Chloride Anhydrous, dissolve completely under normal temperature after adding tetrahydrofuran solvent, then add the porous support activated under normal temperature and make slurries, stir after 2 hours under normal temperature, vacuumize drying at being uniformly heated to 60 DEG C, obtain complex carrier.

Take Nonmetallocene title complex, dissolvedly in methylene dichloride, make uniform solution, this uniform solution joined in described modification complex carrier under normal temperature, uniform stirring makes mixed serum.Stir 4 hours under normal temperature, under normal temperature, vacuum-drying obtains load type non-metallocene catalyst.

Wherein proportioning is, Magnesium Chloride Anhydrous and tetrahydrofuran (THF) proportioning are 0.1mol: 150mL; Magnesium chloride and Nonmetallocene title complex mol ratio are 1: 0.05; Magnesium chloride and chemical processing agent mol ratio are 1: 0.10; The amount ratio of magnesium chloride and porous support is 1mol: 200g; The ratio of Nonmetallocene title complex and methylene dichloride is 0.05 grams per milliliter.

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

Application Example

Catalyzer CAT-1 ~ the CAT-12 obtained in the embodiment of the present invention and CAT-A ~ D carried out respectively under the following conditions in accordance with the following methods homopolymerization, the copolymerization of ethene and prepare ultrahigh molecular weight polyethylene(UHMWPE) polymerization:

Homopolymerization is: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.8MPa, polymerization temperature 85 DEG C, hydrogen partial pressure 0.2MPa, 2 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, then add hydrogen to 0.2MPa, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.8MPa.After reaction terminates, by gas reactor emptying, release still interpolymer, after drying, weigh quality.Particular case and the polymerization evaluation result of this polyreaction are as shown in table 1.

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

Prepare ultrahigh molecular weight polyethylene(UHMWPE) to be polymerized to: 5 liters of polymerization autoclaves, slurry polymerization processes, 2.5 liters of hexane solvents, polymerization stagnation pressure 0.5MPa, polymerization temperature 70 DEG C, 6 hours reaction times.First 2.5 liters of hexanes are joined in polymerization autoclave, open and stir, then add 50mg load type non-metallocene catalyst and catalyst mixture, promotor and active metal mol ratio are 100, finally continue to pass into ethene and make polymerization stagnation pressure constant in 0.5MPa.After reaction terminates, by gas reactor emptying, release still interpolymer, after drying, weigh quality.Particular case and the polymerization evaluation result of this polyreaction are as shown in table 2.

Known by the test-results data of sequence number in table 13 and 4, increase the consumption of promotor, namely improve promotor and catalyst activity metal molar than time, impact that is active on polymerization catalyst and polymer stacks density is not remarkable.It can be said that bright, the load type non-metallocene catalyst adopting method provided by the invention to prepare only needs fewer promotor consumption just can obtain high olefin polymerizating activity; And the polymkeric substance such as obtained polyethylene has excellent polymer morphology and high polymer bulk density thus.

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

Known by the test-results data of sequence number 1 and comparative example sequence number 16 ~ 18 in contrast table 1, reduce or increase the add-on of Nonmetallocene title complex in catalyzer, its activity decreases or increases, and the molecular weight distribution of polymkeric substance also broadens thereupon or narrows.Reduce in catalyzer or increase chemical processing agent, its activity decreases or increases, and the molecular weight distribution of polymkeric substance also narrows thereupon or broadens.Therefore can judge that Nonmetallocene title complex has the effect of the molecular weight distribution that narrows, and chemical processing agent has the effect improving catalyst activity and broadening molecular weight distribution.Therefore researcher in this field knows, can be obtained the catalyzer of different activities and polymer performance by the proportioning of both changes.

Known by the test-results data of sequence number 1 and comparative example sequence number 19 in contrast table 1, the load type non-metallocene catalyst adopting Grignard reagent and halogenating agent to be obtained by reacting has higher polymerization activity than the loaded catalyst obtained without Grignard reagent, the polymkeric substance that catalyzed polymerization obtains has narrower molecular weight distribution, higher bulk density, preferably particle form, thus illustrate adopt the carrier prepared of Grignard reagent can make Nonmetallocene title complex evenly be distributed in carrier inside, thus the performance of Nonmetallocene title complex itself can better be played.And the carrier to be obtained by reacting by Grignard reagent and halogenating agent has better crystal habit, can evenly distribution on porous support, the polymkeric substance of preparation has better form and size distribution, thus reduces the cost in production process.

From table 2, adopt catalyzer provided by the present invention, can prepare ultrahigh molecular weight polyethylene(UHMWPE), its bulk density increases all to some extent, and contrast sequence number 1 and 2 is visible, adopts methylaluminoxane can increase the viscosity-average molecular weight of polymkeric substance as promotor.In contrast table 2, the test-results data of sequence number 1 and comparative example 5 ~ 8 are known, and reduce in catalyzer or increase Nonmetallocene title complex, polymkeric substance viscosity-average molecular weight reduces thereupon or increases.Thus illustrate that Nonmetallocene title complex also has the effect increasing polymkeric substance viscosity-average molecular weight.

By sequence number in table 11 and 14,15, in table 2, the test-results data of sequence number 1 and 3,4 are known, catalyzer is in preparation process, complex carrier is first through helping chemical processing agent process, and then with chemical processing agent contact reacts and the loaded catalyst that finally obtains, and without the loaded catalyst helping chemical processing agent process to obtain, there is higher polymerization activity, polymer stacks density, viscosity-average molecular weight, and slightly narrow molecular weight distribution.

Below second embodiment of the invention is described.

The present invention relates to a kind of preparation method of load type non-metallocene catalyst, comprise the following steps: the first chemical processing agent making to be selected from IVB race metallic compound reacts with the porous support optionally through thermal activation treatment, obtains the step of modifying porous support; Described modification porous support, Grignard reagent and halogenating agent are reacted, obtains the step of complex carrier; The second chemical processing agent and the described complex carrier that make to be selected from described IVB race metallic compound react, and obtain the step of modifying complex carrier; Nonmetallocene title complex is contacted in the presence of the solvent with described modification complex carrier, obtains the step of mixed serum; With mixed serum described in convection drying, obtain the step of described load type non-metallocene catalyst.

According to the present invention, the first chemical processing agent being selected from IVB race metallic compound is reacted with the porous support optionally through thermal activation treatment, obtains and modify porous support.

Below described porous support is specifically described.

Below described chemical processing agent is specifically described.

According to the present invention, using IVB race metallic compound as described first and second chemical processing agent.

M(OR ¹) _mX _nR ² _4-m-n

Wherein:

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

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

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

According to the present invention, make to be selected from the first chemical processing agent of described IVB race metallic compound and describedly optionally react through the porous support of thermal activation treatment, obtaining and modify porous support (reacting I hereinafter referred to as chemical treatment); Or the second chemical processing agent and the complex carrier as described below that make to be selected from described IVB race metallic compound react, obtain modification complex carrier (hereinafter referred to as chemical treatment reaction II) as described below.

According to the present invention, in described chemical treatment reaction I and described chemical treatment reaction II, the first and second respective used chemical processing agent can be the same or different, all independently selected from aforesaid IVB race metallic compound.

In addition, in the context of the present invention, sometimes described first chemical processing agent and described second chemical processing agent are referred to as chemical processing agent and are not distinguished, unless explicitly stated.

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 following content can be enumerated.

When described chemical processing agent is liquid at normal temperatures, can by using described chemical processing agent to the mode of the described chemical processing agent having directly dropping predetermined amount in the reaction object of this chemical processing agent process to be utilized (such as described porous support or described complex carrier).

As carrying out described chemically treated method, such as can enumerate, when chemical processing agent is solid-state (such as zirconium tetrachloride), first the solution of described chemical processing agent is prepared, then in pending reaction object (such as described porous support or described complex carrier), the described solution of (preferably dripping) the described chemical processing agent containing predetermined amount is added, to carry out chemical treatment reaction.When chemical processing agent is liquid (such as titanium tetrachloride), directly the described chemical processing agent of predetermined amount can be added in (preferably dripping) pending reaction object (such as described porous support or described complex carrier), to carry out chemical treatment reaction, or after this chemical processing agent is prepared into solution, the described solution of (preferably dripping) the described chemical processing agent containing predetermined amount is added, to carry out chemical treatment reaction in pending reaction object (such as described porous support or described complex carrier).

After chemical treatment reaction terminates, by filtering, washing and drying, can obtain through chemically treated product.

Namely, according to the present invention, after the reaction of described first and second chemical processing agent of use terminates, by aforesaid filtration, washing and drying, obtained process product is separated completely, and then uses this process product to carry out next step reaction or process.

So far, by aforesaid chemical treatment reaction I, modification porous support is obtained.

Then, described modification porous support, Grignard reagent and halogenating agent are reacted, obtain complex carrier.

Below described Grignard reagent is specifically described.

As described dialkyl magnesium, dimethyl magnesium (Mg (CH such as can be enumerated ₃) ₂), magnesium ethide (Mg (CH ₃cH ₂) ₂), dipropyl magnesium (Mg (C ₃h ₇) ₂), diisobutyl magnesium (Mg (i-C ₄h ₉) ₂), di-n-butyl magnesium (Mg (C ₄h ₉) ₂), diisoamyl magnesium (Mg (i-C ₅h ₁₁) ₂), two n-pentyl magnesium (Mg (C ₅h ₁₁) ₂), dihexyl magnesium (Mg (C ₆h ₁₃) ₂), two isohexyl magnesium (Mg (i-C ₆h ₁₃) ₂), methylethyl magnesium (Mg (CH ₃cH ₂) (CH ₃)), diphenyl magnesium (Mg (C ₆h ₅) ₂) and dibenzyl magnesium (Mg [CH ₂(C ₆h ₅)] ₂) etc., wherein preferred dimethyl magnesium, magnesium ethide, diisobutyl magnesium, dicyclohexyl magnesium, diphenyl magnesium and dibenzyl magnesium, most preferably dimethyl magnesium, magnesium ethide and diphenyl magnesium.

According to the present invention, in order to obtain described complex carrier, the reaction of described modification porous support, described Grignard reagent and described halogenating agent is generally made to carry out under the existence of solvent (hereinafter sometimes referred to dissolving Grignard reagent solvent or the first solvent).To now used solvent, there is no particular limitation, as long as it can dissolve this Grignard reagent and this halogenating agent and with them, chemical reaction not occur.

According to the present invention, to reactive mode under solvent (the first solvent) exists of described modification porous support, Grignard reagent and halogenating agent, there is no particular limitation.Such as can enumerate, (now respective used dissolving Grignard reagent solvent can be identical for the solution (as required) of the solution first utilizing aforementioned dissolving Grignard reagent solvent to prepare described Grignard reagent respectively and described halogenating agent, also can be different), then in described grignard reagent solution successively or be metered into simultaneously or drip described modification porous support and described halogenating agent or halogenating agent solution, or simultaneously or the mode of successively metering mixing described modification porous support, described grignard reagent solution and described halogenating agent solution; Or, described modification porous support, described Grignard reagent and described halogenating agent are measured interpolation (preferably dripping) to the mode etc. in described dissolving Grignard reagent solvent simultaneously or successively, but are not limited to this.Wherein, preferred elder generation prepares described grignard reagent solution as previously mentioned, then be metered into described modification porous support wherein, obtain mixed serum, then halogenating agent or halogenating agent solution measures are added (preferably dripping) to the mode in described mixed serum.

According to the present invention, in order to manufacture described complex carrier, such as can at normal temperature at the temperature lower than the boiling point of used any solvent, the reaction under the first solvent exists of modification porous support, Grignard reagent and halogenating agent is made to carry out 0.5-48h altogether, preferred 1-24h, optimum 2-8h (if desired by stirring).

Then, by reacting II according to the mode described by aforesaid chemical treatment above, making described second chemical processing agent being selected from described IVB race metallic compound carry out chemical reaction with the complex carrier obtained, obtaining thus and modify complex carrier.

As previously mentioned, after the reaction of described second chemical processing agent of use terminates, by aforesaid filtration, washing and drying, obtained modification complex carrier is separated completely, and then use this modification complex carrier to carry out next step reaction or process.

In above all chemical structural formulas,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

→ represent singly-bound or double bond;

-represent covalent linkage or ionic linkage;

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

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

According to the present invention's special embodiment, the preparation method of load type non-metallocene catalyst of the present invention is also included in and makes before described second chemical processing agent and described complex carrier react, by the step (pre-treatment step) helping complex carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

Al(R) ₃

Through described pre-treatment step, obtain thus through pretreated complex carrier.Then, then carry out reacting with aforementioned same chemical treatment with described second chemical processing agent according to aforementioned identical mode, just described complex carrier is replaced with described through pretreated complex carrier.

Namely, by reacting with aforementioned same chemical treatment, make to be selected from the second chemical processing agent of described IVB race metallic compound and describedly react to manufacture modification complex carrier through pretreated complex carrier, and manufacturing load type non-metallocene catalyst of the present invention according to mode same before further.

According to the present invention, in described chemical treatment reaction I and described chemical treatment reaction II, the consumption of described first chemical processing agent and described second chemical processing agent can be the same or different, select independently of one another, thus make in the described Grignard reagent (solid) of Mg element independently and reach 1: 0.01-1 in the mol ratio of described first chemical processing agent of IVB race metal (such as Ti) element or described second chemical processing agent, preferably 1: 0.01-0.50, more preferably 1: 0.05-0.30.

Al(R) ₃

Al(R) _nX _3-n

Embodiment

Mv＝5.37×10 ⁴×[η] ^1.37

Wherein, η is limiting viscosity.

Embodiment 1

Grignard reagent adopts methylmagnesium-chloride (MeMgCl), and dissolve Grignard reagent solvent and adopt tetrahydrofuran (THF), halogenating agent adopts n-propylcarbinyl chloride, porous support adopts silicon-dioxide, i.e. silica gel, model is the ES757 of Ineos company, and Nonmetallocene title complex employing structure is compound, first and second chemical processing agent all adopts titanium tetrachloride, second solvent adopt methylene dichloride.

Silica gel after heat-obtaining activation, adds 100ml hexane, adds the first chemical processing agent under stirring at normal temperature condition, after reacting 2h, filters, hexanes wash 3 times, each hexane consumption 100ml at 60 DEG C, and last normal-temperature vacuum is drained and obtained modifying porous support.

Form homogeneous slurries by joining under modification porous support normal temperature in grignard reagent solution (containing 0.1mol Grignard reagent), be added drop-wise to by halogenating agent under stirring at normal temperature in these homogeneous slurries, time for adding is 30 minutes.After being added dropwise to complete, stir 2 hours under normal temperature.Solid collected by filtration component, solid ingredient hexanes wash 2 times, each hexane consumption 60ml, at 60 DEG C, vacuum-drying obtains complex carrier.

Then in complex carrier, add 60ml hexane, drip the second chemical processing agent, stirring reaction 4 hours at 60 DEG C with 30 minutes under agitation at normal temperatures, filter, hexanes wash 2 times, each hexane consumption 60ml, under normal temperature, vacuum-drying obtains modifying complex carrier.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 1000mL, Grignard reagent and halogenating agent mol ratio are 1: 1; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.05; The mol ratio of Grignard reagent and twice chemical processing agent is 1: 0.10; The amount ratio of Grignard reagent and porous support is 1mol: 200g; The ratio of Nonmetallocene title complex and the second solvent is 0.05 grams per milliliter.

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

Embodiment 2

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

Grignard reagent adopts ethylmagnesium chloride (EtMgCl), and dissolve Grignard reagent solvent and adopt ether, halogenating agent adopts chloric ethane, and Nonmetallocene title complex adopts porous support changes into 955 type silica gel of Grace company, 400 DEG C, continue roasting 8h and thermal activation under nitrogen atmosphere, the second solvent adopts trichloromethane.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 500mL, Grignard reagent and halogenating agent mol ratio are 1: 2; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.1; Grignard reagent and twice chemical processing agent mol ratio are 1: 0.20; The amount ratio of Grignard reagent and porous support is 1mol: 100g; The ratio of Nonmetallocene title complex and the second solvent is 0.15 grams per milliliter.

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

Embodiment 3

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

Grignard reagent changes into ethylmagnesium bromide (EtMgBr), and dissolve Grignard reagent solvent and adopt n-butyl ether, Nonmetallocene title complex adopts halogenating agent adopts monobromethane, and first and second chemical processing agent all adopts titanium tetrabromide (TiBr4), and porous support adopts aluminium sesquioxide.By aluminium sesquioxide 700 DEG C, continue roasting 6h under nitrogen atmosphere, the second solvent adopts benzene.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 1500mL; Grignard reagent and halogenating agent mol ratio are 1: 1.5; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.2; Grignard reagent and twice chemical processing agent mol ratio are 1: 0.30; The amount ratio of Grignard reagent and porous support is 1mol: 500g; The ratio of Nonmetallocene title complex and the second solvent is 0.08 grams per milliliter.

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

Embodiment 4

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

Grignard reagent changes into phenyl-magnesium-chloride (C ₆h ₅mgCl), dissolve Grignard reagent solvent and adopt tetrahydrofuran (THF), Nonmetallocene title complex adopts halogenating agent adopts chlorobenzene, and first and second chemical processing agent all adopts tetraethyl-titanium (Ti (CH ₃cH ₂) ₄), porous support adopts polynite.By polynite 400 DEG C, continue roasting 8h under nitrogen atmosphere, the second solvent adopts toluene.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 600mL; Grignard reagent and halogenating agent mol ratio are 1: 1.1; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.04; Grignard reagent and twice chemical processing agent mol ratio are 1: 0.05; The amount ratio of Grignard reagent and porous support is 1mol: 50g; The ratio of Nonmetallocene title complex and the second solvent is 0.30 grams per milliliter.

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

Embodiment 5

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

Grignard reagent changes into methyl-magnesium-bromide (CH ₃mgBr), dissolve Grignard reagent solvent and adopt Isosorbide-5-Nitrae-dihydro six ring, Nonmetallocene title complex adopts halogenating agent adopts bromocyclohexane, and first and second chemical processing agent all adopts tetra-n-butyl titanium (Ti (C ₄h ₉) ₄), porous support adopts the polystyrene of partial cross-linked (degree of crosslinking is 30%).By this polystyrene 100 DEG C, continue under nitrogen atmosphere to dry 12h, the second solvent adopts ethylbenzene.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 2500mL; Grignard reagent and halogenating agent mol ratio are 1: 1.5; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.30; Grignard reagent and twice chemical processing agent mol ratio are 1: 0.50; The amount ratio of Grignard reagent and porous support is 1mol: 2000g; The ratio of Nonmetallocene title complex and the second solvent is 0.10 grams per milliliter.

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

Embodiment 6

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

Grignard reagent changes into benzylmagnesium chloride (Mg (PhCH ₂) Cl), dissolve Grignard reagent solvent and adopt ethyl n-propyl ether, Nonmetallocene title complex adopts halogenating agent adopts Benzyl Chloride, and first and second chemical processing agent all adopts tetraethyl-zirconium (Zr (CH ₃cH ₂) ₄), porous support adopts diatomite, by diatomite 500 DEG C, continue roasting 8h under nitrogen atmosphere.

Wherein proportioning is, in the described Grignard reagent of Mg element with dissolve the proportioning of Grignard reagent solvent for 1mol: 667mL; Grignard reagent and Nonmetallocene title complex mol ratio are 1: 0.10; Grignard reagent and twice chemical processing agent mol ratio are 1: 0.10; The amount ratio of Grignard reagent and porous support is 1mol: 200g.

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

Embodiment 7

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

Grignard reagent changes into cyclohexyl magnesium chloride (Mg (C ₆h ₁₁) Cl), dissolve Grignard reagent solvent and adopt ether, Nonmetallocene title complex adopts halogenating agent adopts chlorocyclohexane, and first and second chemical processing agent all adopts purity titanium tetraethoxide (Ti (OCH ₃cH ₂) ₄).

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

Embodiment 8

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

Grignard reagent changes into magnesium ethide (Mg (C ₂h ₅) ₂), dissolve Grignard reagent solvent and adopt ether, Nonmetallocene title complex adopts halogenating agent adopts chloro normal hexane, and first and second chemical processing agent all adopts isobutyl-titanous chloride (Ti (i-C ₄h ₉) Cl ₃).

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

Embodiment 9

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

Grignard reagent changes into dihexyl magnesium (Mg (C ₆h ₁₃) ₂), dissolve Grignard reagent solvent and adopt ether, first and second chemical processing agent all adopts three isobutoxy titanium chloride (TiCl (i-OC ₄h ₉) ₃).

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

Embodiment 10

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

Grignard reagent changes into ethyl normal-butyl magnesium (Mg (C ₄h ₉) (C ₂h ₅)), dissolve Grignard reagent solvent and adopt ether, first and second chemical processing agent all adopts dimethoxy zirconium dichloride (ZrCl ₂(OCH ₃) ₂).

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

Embodiment 11

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

Load type non-metallocene catalyst is designated as CAT-11.

Embodiment 12

Substantially the same manner as Example 11, but have following change:

Load type non-metallocene catalyst is designated as CAT-12.

Comparative example A

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

The mol ratio of Grignard reagent and the first and second chemical processing agent all changes into 1: 0.20.

Catalyzer is designated as CAT-A.

Comparative example B

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

Catalyzer is designated as CAT-B.

Comparative example C

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

Catalyzer is designated as CAT-C.

Comparative example D

Silica gel after heat-obtaining activation, adds 60ml hexane, adds the first chemical processing agent under stirring at normal temperature condition, after reacting 2h, filters, hexanes wash 3 times, each 60ml at 60 DEG C, and at 60 DEG C, vacuum is drained and obtained modifying porous support.

Take 0.1mol Magnesium Chloride Anhydrous, dissolve completely under normal temperature after adding tetrahydrofuran solvent, then add modification porous support under normal temperature and make slurries, stir after 2 hours under normal temperature, vacuumize drying at being uniformly heated to 60 DEG C, obtain complex carrier.

Wherein proportioning is, Magnesium Chloride Anhydrous and tetrahydrofuran (THF) proportioning are 0.1mol: 150mL; Magnesium chloride and Nonmetallocene title complex mol ratio are 1: 0.05; The mol ratio of magnesium chloride and twice chemical processing agent is 1: 0.10; The amount ratio of magnesium chloride and porous support is 1mol: 200g; The ratio of Nonmetallocene title complex and methylene dichloride is 0.05 grams per milliliter.

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

Comparative example E

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

Omit the step obtaining and modify porous support, that is, replace described modification porous support with the porous support after thermal activation, prepare load type non-metallocene catalyst similarly to Example 1.

Catalyzer is designated as CAT-E.

Application Example

Catalyzer CAT-1 ~ the CAT-12 obtained in the embodiment of the present invention and CAT-A ~ E carried out respectively under the following conditions in accordance with the following methods homopolymerization, the copolymerization of ethene and prepare ultrahigh molecular weight polyethylene(UHMWPE) polymerization:

By sequence number in table 11 and 20, in table 2, the test-results data of sequence number 1 and 9 are known, porous support first carries out through chemical processing agent process the loaded catalyst that follow-up supported operation obtains again, with the loaded catalyst obtained without chemical processing agent process, there is higher polymerization activity and polymer stacks density.

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

At this, contriver wishes to carry out following explanation with regard to the difference of Ziegler-Natta catalyst (electron donor especially wherein related to), metallocene catalyst and non-metallocene catalyst.

It is well known in the art that Ziegler-Natta catalyst, metallocene catalyst and non-metallocene catalyst belong to different catalyst systems.First, Ziegler-Natta catalyst belongs to multicenter catalyzer, and non-metallocene catalyst is the same with metallocene catalyst, belongs to single-site catalysts.

Textbook (" Catalysts for Olefin Polymerization and polyolefine ", Xiao Shijing, the raw work of remaining tax, press of Beijing University of Technology, in December, 2002, this textbook is that the academic works publishing fund of China national science and technology subsidizes " 15 " state key books) at its 7th page, metallocene catalyst is defined, namely " metallocene catalyst is normally by transition metal (main employing IVB race element ti, Zr, Hf) and at least 1 cyclopentadiene or cyclopentadiene derivant be the complex compound that part is formed ", and describe at its 8th page and " have the performance characteristics different from Ziegler-Natta catalyst system just because of metallocene catalyst system, since the eighties in 20th century, the investigation and application of metallocene catalyst achieves huge progress ".Also non-metallocene catalyst is defined at the 8th page, i.e. " so-called non-metallocene catalyst refers to not containing the compound of the non-cyclopentadienyl ligand transition metal of cyclopentadiene group; there is energy catalysis in olefine polymerization in promotor methylaluminoxane ", or " non-metallocene compound mainly forms the cationic ligand similar to cyclopentadienyl with the C atom on the hybrid atom MCM-41 cyclopentadiene such as B, P, N or other aromatic rings, forms non-metallocene compound with IVB race metal (Ti, Zr, Hf) coordination ".

US Patent No. 5244855 discloses a kind of manufacture method of loaded catalyst, this manufacture method comprises diether compounds (the such as 2-isopentyl-2-sec.-propyl-1 using inert polymer carrier, magnesium halide, titanium tetrachloride and following structure, 3-Propanal dimethyl acetal, i.e. DMP, uses as electron donor) as raw material.

Aforesaid textbook (" Catalysts for Olefin Polymerization and polyolefine ", Xiao Shijing, the raw work of remaining tax, press of Beijing University of Technology, in December, 2002) be recorded " entering the nineties in 20th century; occurred with 1; 3-bis-ethers is the Ziegler-Natta carrier model effective catalyst of new generation of internal electron donor synthesis ", " due to two ethers electron donor and MgCl at its 6th page ₂carrier coordination ability is very strong, in catalyst synthesis processes, can not further with TiCl ₄reaction ... ".This textbook is recorded " MgCl at its 21st page ₂carrier model titanium (Mg-Ti) catalyzer is except carrier (MgCl ₂) and active ingredient (Ti compound) outward, also containing internal electron donor compound (Di) ".This textbook is recorded " in the evolution at Ziegler-Natta catalyst, the application of electron donor plays very important effect ", " MgCl at its 72nd page ₂after carried catalyst appearance, the effect of electron donor seems even more important, now become the important component that Ziegler-Natta catalyst system cannot lack " and " in recent years, be used as catalyzer MgCl prepared by internal electron donor with 1.3-diether compounds (DE) ₂/ TiCl ₄/ DE, when need not external electron donor, " this textbook gives the structure of a kind of diether compounds being used as electron donor at its 100th page, roughly the same with the diether compounds involved by US Patent No. 5244855.This fact shows, the final manufactured loaded catalyst of US Patent No. 5244855 is Ziegler-Natta carrier model effective catalyst.

Aforesaid textbook is also recorded " due to two ethers electron donor and MgCl at its 6th page ₂carrier coordination ability is very strong, in catalyst synthesis processes, can not further with TiCl ₄reaction ... ".Therefore, DMP or the diether compounds involved by US Patent No. 5244855 do not react with titanium tetrachloride, so not corresponding to the Nonmetallocene part alleged by this area.

Claims

Make optionally to react with halogenating agent through the porous support of thermal activation treatment and/or the optional chemical processing agent process through being selected from IVB race metallic compound, Grignard reagent, the step of acquisition complex carrier;

Mixed serum described in convection drying, obtains the step of described load type non-metallocene catalyst,

Wherein said preparation method is optionally also included in and makes before described chemical processing agent and described complex carrier react, by the step helping complex carrier described in chemical processing agent pre-treatment being selected from aikyiaiurnirsoxan beta, aluminum alkyls or its arbitrary combination.

2. according to preparation method according to claim 1, it is characterized in that, described halogenating agent is selected from chloro C _1-30hydrocarbon and bromo C _1-30one or more in hydrocarbon, wherein said C _1-30hydrocarbon is C _1-30alkane, C _2-30alkene, C _6-30aromatic hydrocarbons, C _7-30aralkyl hydrocarbon or C _7-30alkane aromatic hydrocarbons.

3., according to preparation method according to claim 2, it is characterized in that, described halogenating agent be selected from monobromethane, monochloroethane, monobromethane, 1-chloro-butane, 1-chloro-hexane, chlorobenzene, bromobenzene and benzyl chloride one or more.

4. according to preparation method according to claim 1, it is characterized in that, it is one or more in the dialkyl magnesium of (R) (R ') Mg that described Grignard reagent is selected from alkyl magnesium halide that general formula is RMgX and general formula, wherein radicals R and R ' are same to each other or different to each other, and are C independently of one another ₁-C ₃₀alkyl, C ₂-C ₃₀thiazolinyl, C ₆-C ₃₀aryl, C ₇-C ₃₀alkaryl or C ₇-C ₃₀aralkyl, X is halogen.

5., according to preparation method according to claim 4, it is characterized in that, described Grignard reagent be selected from methylmagnesium-chloride, ethylmagnesium chloride, phenyl-magnesium-chloride, benzylmagnesium chloride, dimethyl magnesium, magnesium ethide and diphenyl magnesium one or more.

6. according to preparation method according to claim 1, it is characterized in that, described solvent is selected from C _6-12aromatic hydrocarbon, halo C _6-12aromatic hydrocarbon, halo C _1-10one or more in alkane, ester and ether.

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

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

In above chemical structural formula,

Q is 0 or 1;

D is 0 or 1;

M is 1,2 or 3;

M is selected from periodic table of elements III-th family to XI race atoms metal;

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

D is selected from nitrogen-atoms, Sauerstoffatom, sulphur atom, selenium atom, phosphorus atom, nitrogen-containing group, phosphorus-containing groups, C ₁-C ₃₀alkyl, sulfuryl or sulfoxide group, wherein N, O, S, Se and P are coordination atom separately;

→ represent singly-bound or double bond;

-represent covalent linkage or ionic linkage;

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

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

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

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

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

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

Described C ₁-C ₃₀alkyl is selected from C ₁-C ₃₀alkyl, C ₇-C ₃₀alkaryl, C ₇-C ₃₀aralkyl, C ₃-C ₃₀cyclic alkyl, C ₂-C ₃₀thiazolinyl, C ₂-C ₃₀alkynyl, C ₆-C ₃₀aryl or C ₈-C ₃₀condensed ring radical;

The C of described replacement ₁-C ₃₀alkyl is selected from one or more aforementioned halogen or aforementioned C ₁-C ₃₀the aforementioned C of alkyl alternatively base ₁-C ₃₀alkyl;

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

Described silicon-containing group is selected from-SiR ⁴²r ⁴³r ⁴⁴;

Described germanic group is selected from-GeR ⁴⁶r ⁴⁷r ⁴⁸;

The described tin group that contains is selected from-SnR ⁵⁰r ⁵¹r ⁵²or-T-Sn (O) R ⁵⁴, wherein said group T ditto defines,

Described Ar represents C ₆-C ₃₀aryl, and

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

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

In chemical structural formulas all above,

F is selected from nitrogen-atoms, nitrogen-containing group or phosphorus-containing groups, and wherein N and P is coordination atom separately.

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

In chemical structural formulas all above,

Y is selected from-NR ²³r ²⁴,-N (O) R ²⁵r ²⁶,-PR ²⁸r ²⁹, hydroxyl ,-OR ³⁴,-SR ³⁵,-S (O) R ³⁶,-SeR ³⁸or-Se (O) R ³⁹, wherein N, O, S, Se and P are coordination atom separately;

R ⁴, R ⁶to R ²¹be selected from hydrogen or C independently of one another ₁-C ₃₀alkyl, and

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

11., according to preparation method according to claim 10, is characterized in that, described Nonmetallocene title complex be selected from the compound with following chemical structural formula one or more:

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

13. according to preparation method according to claim 1, it is characterized in that, the mol ratio of described Grignard reagent and described halogenating agent is 1: 1-100, in the mol ratio of the described Grignard reagent of Mg element and described Nonmetallocene title complex for 1: 0.0001-1, the amount ratio of described Grignard reagent and described porous support is 1mol: 10-2000g, in the described Grignard reagent of Mg element and to help the mol ratio of chemical processing agent for 1: 0-1.0 described in Al element, and in the described Grignard reagent of Mg element with the mol ratio of the described chemical processing agent of IVB race elemental metal for 1: 0.01-1.

14., according to preparation method according to claim 1, is characterized in that, described IVB race metallic compound be selected from IVB race metal halide one or more.

15., according to preparation method according to claim 14, is characterized in that, described IVB race metallic compound is selected from TiCl ₄and ZrCl ₄in one or more.

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

17. according to preparation method according to claim 16, it is characterized in that, described porous support be selected from partial cross-linked styrene polymer, silicon-dioxide, aluminum oxide, magnesium oxide, oxidation sial, oxidation magnalium, titanium dioxide, molecular sieve and polynite one or more.

18. 1 kinds of load type non-metallocene catalysts, it manufactures by according to the preparation method described in any one of claim 1-17.

19. 1 kinds of alkene homopolymerization/copolymerization methods, it is characterized in that, with according to load type non-metallocene catalyst according to claim 18 for Primary Catalysts, to be selected from one or more in aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and boron alkyl ammonium salt for promotor, make alkene homopolymerization or copolymerization.