CN101412768B - Magnesium compound load type non-metallocene catalyst and preparation thereof - Google Patents

Magnesium compound load type non-metallocene catalyst and preparation thereof Download PDF

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CN101412768B
CN101412768B CN2007101626760A CN200710162676A CN101412768B CN 101412768 B CN101412768 B CN 101412768B CN 2007101626760 A CN2007101626760 A CN 2007101626760A CN 200710162676 A CN200710162676 A CN 200710162676A CN 101412768 B CN101412768 B CN 101412768B
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magnesium compound
metallocene catalyst
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load type
preparation
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CN101412768A (en
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顾越峰
姚小利
李传峰
马忠林
王亚明
陈韶辉
李晓强
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Sinopec Yangzi Petrochemical Co Ltd
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Sinopec Yangzi Petrochemical Co Ltd
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Priority to EP08841802.5A priority patent/EP2202246B1/en
Priority to PCT/CN2008/001739 priority patent/WO2009052701A1/en
Priority to US12/671,654 priority patent/US8716416B2/en
Priority to KR1020107003494A priority patent/KR101206940B1/en
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Abstract

The invention relates to a magnesium compound supported non-metallocene catalyst, which is obtained by directly contacting a non-metallocene ligand and a magnesium compound containing transition metal through an in-situ supporting method. The preparation method for the magnesium compound supported non-metallocene catalyst has simple and feasible process, and the supporting capacity and the polymerization activity of the catalyst have wide adjustable range. When the magnesium compound supported non-metallocene catalyst is combined with a catalyst promoter to catalyze the homopolymerization/copolymerization of olefins, high polymerization activities of the olefins can be obtained only by using small amount of the catalyst promoter.

Description

A kind of magnesium compound load type non-metallocene catalyst and preparation method thereof
Technical field
The present invention relates to a kind of for olefines polymerization load type non-metallocene catalyst.Particularly, the present invention relates to a kind of magnesium compound load type non-metallocene catalyst, it is through original position load method the Nonmetallocene part directly to be contacted with the magnesium compound that contains catalytically-active metals to obtain.Through with the combination of promotors such as magnesium compound load type non-metallocene catalyst of the present invention and aikyiaiurnirsoxan beta or aluminum alkyls, can be used for the homopolymerization or the copolymerization of catalyzed alkene.
Background technology
The non-metallocene catalyst that the middle and later periods nineties 20th century occurs; Be called luxuriant rear catalyst again; The central atom of Primary Catalysts has comprised nearly all transition metal; Be after Ziegler, Ziegler-Natta and metallocene catalyst the 4th generation olefin polymerization catalysis, such catalyzer has reached on some performance or even has surpassed metallocene catalyst.Non-metallocene catalyst does not contain cyclopentadienyl group; Ligating atom is oxygen, nitrogen, sulphur and phosphorus; It is characterized in that central ion has stronger Electron Affinities, and have cis alkyl or halogen metal division center, carry out alkene insertion and σ-key easily and shift; The easy alkylation of central metal helps the generation at cation activity center; The title complex that forms has the geometric configuration of qualification, stereoselectivity, electronegativity and chirality controllability.In addition, the metal-carbon key of formation polarizes easily, is beneficial to the polymerization of alkene.Therefore, even under higher polymeric reaction temperature, also can obtain the olefin polymer of higher molecular weight.
But homogenous olefin polymerization catalyst has been proved it in olefinic polyreaction has active duration short, sticking still, high MAO consumption easily, and obtains the too low or too high weak point of polymericular weight, has seriously limited its industrial application.
A kind of alkene homopolymerization/catalyst for copolymerization or catalystsystem that patent ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207 are prepared; Has alkene homopolymerization/copolymerization performance widely; Be applicable to the polymerization technique of various ways; But need higher promotor consumption at the disclosed catalyzer of this patent or catalystsystem during in olefinic polymerization, could obtain suitable olefin polymerizating activity, and exist in the polymerization process and glue the still phenomenon.
Common way is that non-metallocene catalyst is technological through certain loadization, processes loaded catalyst, thereby improves the polymerization of alkene and the particle form of resulting polymers.It shows as the initial activity that has suitably reduced catalyzer to a certain extent; Prolong the polymerization activity life-span of catalyzer; Reduce even avoided the caking in the polymerization process or gathered phenomenon cruelly, improve the form of polymkeric substance, improve the apparent density of polymkeric substance; Can make it satisfy more polymerization technique process, like vapour phase polymerization or slurry polymerization etc.
To the disclosed non-metallocene catalyst of patent ZL01126323.7, ZL02151294.9, ZL02110844.7 and WO03/010207; Patent CN1539855A, CN1539856A, CN1789291A, CN1789292A, CN1789290A, WO/2006/063501,200510119401.x etc. have adopted variety of way to carry out load; Obtain load type non-metallocene catalyst; But these patents all relate to the Nonmetallocene organic cpds that contains transition metal (or being called non-metallocene catalyst or Nonmetallocene title complex) are carried on the carrier after the processing; The non-metallocene catalyst charge capacity is lower, or it combines not really tight with carrier.
Existing olefin polymerization catalysis patent is mostly based on metallocene catalyst; Like US4808561, US5240894, CN1049439, CN1136239, CN1344749, CN1126480, CN1053673, CN1307594, CN1130932, CN1103069, CN1363537, CN1060179, US574417, EP685494, US4871705 and EP0206794 etc., but these patents also all relate to the metallocene catalyst that contains transition metal are carried on the carrier after the processing.
Patent EP708116 discloses the zirconium tetrachloride that makes gasification earlier and under 160～450 ℃ of temperature, has contacted and load with carrier; Again the zirconium tetrachloride of load is obtained carried metallocene catalyst with the lithium salts reaction of part, then through cooperate the polymerization that is used for alkene with promotor.The problem that this catalyzer exists is that load process requires high temperature, and high vacuum is not suitable for industrial production.
Patent ZL01131136.3 discloses a kind of method of synthetic carried metallocene catalyst.Silica gel is mixed in solvent with IVB group 4 transition metal halogenide, direct again and part negative ion reaction, thus in a step, realize synthesizing and load of metallocene catalyst.But it is 1: 1 that this method requires the transition metal and the mol ratio of part, and needs adding proton donor, and like butyllithium etc., and the part that is adopted is the metallocene part that contains cyclopentadienyl group of bridging type or non-bridging type.
The grade of Xiao Yi is open " novel Ni (acac) in paper 2/ TiCl 4The poly research of/L ligand complex catalyst catalyzed ethylene polymerization for preparing branched " (Zhongshan University's journal: natural science edition, 2003,42 (3): 28), it is with anhydrous MgCl 2, Ni (acac) 2And L, be dissolved in the tetrahydrofuran-ethyl alcohol mixed solvent after, add people's silica gel stirring reaction, add a certain amount of titanium tetrachloride and continue reaction, add a certain amount of Et again 2A1C1 reaction, drain catalyzer, having prepared with magnesium chloride-silica gel thus is carrier, the Ni (acac) that modifies with the alpha-diimine ligand L 2/ TiCl 4Composite catalyst.Adopt this catalyst list-vinyl polymerization can obtain branched polyethylene, wherein ligand L 2 makes the branched polyethylene that the degree of branching is 4-12 side chain number/1000C.
Though can polymerization obtain the good polymkeric substance of particle form as the carrier of non-metallocene catalyst with silica-gel carrier or with the complex carrier that contains silica gel; And can the controlling polymers size distribution; But the polymerization activity of catalyzer is lower; Owing to contain silica gel in the ash, limited the practical use of polymkeric substance.
There is bibliographical information to adopt the chloro aluminium triethyl to handle MgCl 2(THF) 2, and the load bis cyclopentadienyl zirconium dichloride, make carried metallocene catalyst thus.Its process is: magnesium chloride is dissolved in the THF, handles final load bis cyclopentadienyl zirconium dichloride (EUROPEAN POLYMER JOURNAL, 2005,41,941～947) after the hexane washing of precipitate with the chloro aluminium triethyl.
Sun Min etc. are open in paper, and " in-situ reaction prepares CpTi (dbm) Cl 2/ MgCl 2The research of supported catalyst and catalyzed ethylene polymerization thereof " (the polymer journal, 2004, (1): 138), it adopts the Grignard reagent legal system to be equipped with magnesium chloride support, adds CpTi (dbm) Cl simultaneously 2, prepare CpTi (dbm) Cl with this 2/ MgCl 2Supported catalyst.The alkylation and the loadization of catalyzer were accomplished in a step, significantly reduced the Preparation of catalysts operation.
Patent CN200510080210.7 discloses original position synthetic supported type vanadium non-metallocene catalyst and preparation method and application; Wherein earlier dialkyl magnesium is formed acyl group naphthols magnesium or beta-diketon magnesium compound with acyl group naphthols or beta-diketon reaction; Muriate with the tetravalence vanadium reacts again, forms carrier and active catalytic components simultaneously.
Patent CN200610026765.8 discloses one type of single active center's Z-N olefin polymerization catalysis.This catalyzer with the salicylic aldehyde that contains coordinating group or substituted salicylaldehyde derivatives as electron donor; Be through in magnesium compound (like magnesium chloride)/tetrahydrofuran solution, adding through pretreated carrier (like silica gel); Metallic compound (like titanium tetrachloride) and this electron donor obtain after the processing.
Patent CN200610026766.2 is similar with it, discloses one type and has contained heteroatomic organic cpds and the application in Ziegler-Natta catalyst thereof.
Even so, the ubiquitous problem of the load type non-metallocene catalyst that exists in the prior art is that olefin polymerizating activity is low, and in order to improve its activity, just must assist higher promotor consumption.And prior art has been owing to adopted silica gel etc. as load carriers, therefore through containing ash in the polymkeric substance that polymerization obtained, thereby limited the practical use of polymkeric substance.In addition, when adopting the load type non-metallocene catalyst of prior art, polymkeric substance such as resulting Vilaterm have lower polymer stacks density.
Therefore, still need a kind of load type non-metallocene catalyst, its preparation method is simple, is fit to suitability for industrialized production, and can overcomes those problems that exist in the prior art load type non-metallocene catalyst.
Summary of the invention
For this reason, the objective of the invention is to provide on the basis of existing technology a kind of magnesium compound load type non-metallocene catalyst, it is through original position load method the Nonmetallocene part directly to be contacted with the magnesium compound that contains transition metal to obtain.In its preparation process, need not the proton donor and electron donor etc., also need not harsh reaction requirement and reaction condition.Therefore, the preparation method of this loaded catalyst is simple, and is very suitable for suitability for industrialized production.
Particularly, the present invention relates to the content of following aspect:
1. the preparation method of a magnesium compound load type non-metallocene catalyst; It may further comprise the steps: magnesium compound is contacted with the chemical processing agent that is selected from IVB family metallic compound; Obtain the step of product of contact; With handle said product of contact with the Nonmetallocene part, obtain the step of said load type non-metallocene catalyst.
2, according to the preparation method of aspect 1 described magnesium compound load type non-metallocene catalyst, also be included in before said chemical processing agent contacts, handle the step of said magnesium compound with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and its mixture.
According to the preparation method of aspect 1 or 2 described magnesium compound load type non-metallocene catalysts, it is characterized in that 3, said magnesium compound is through modification.
4, according to the preparation method of aspect 3 described magnesium compound load type non-metallocene catalysts; It is characterized in that said modification magnesium compound is to make it to precipitate with solvent and obtain through in by said magnesium compound and solution that THF-pure mixed solvent constitutes, adding deposition.
5, according to the preparation method of aspect each described magnesium compound load type non-metallocene catalyst of 1-4; It is characterized in that; Also comprise through filtering and washing, perhaps without filtration and washing, and the step of the load type non-metallocene catalyst that convection drying obtained.
6. according to the preparation method of aspect each described magnesium compound load type non-metallocene catalyst of 1-5, it is characterized in that said treatment step carries out in the presence of the solvent of the said Nonmetallocene part of solubilized.
7. according to the preparation method of aspect 6 described magnesium compound load type non-metallocene catalysts; It is characterized in that the solvent of the said Nonmetallocene part of said solubilized is selected from one or more in alkane, naphthenic hydrocarbon, halogenated alkane, halo naphthenic hydrocarbon, aromatic hydrocarbon and the halogenated aromatic.
8. according to the preparation method of aspect 7 described magnesium compound load type non-metallocene catalysts, it is characterized in that the solvent of the said Nonmetallocene part of said solubilized is selected from one or more in alkane, halogenated alkane and the aromatic hydrocarbon.
9. according to the preparation method of aspect 8 described magnesium compound load type non-metallocene catalysts, it is characterized in that the solvent of the said Nonmetallocene part of said solubilized is selected from one or more in hexane, methylene dichloride and the toluene.
10. according to the preparation method of aspect each described magnesium compound load type non-metallocene catalyst of 1-9; It is characterized in that said magnesium compound is selected from one or more in magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and the alkyl alkoxy magnesium.
11. the preparation method according to aspect 10 described magnesium compound load type non-metallocene catalysts is characterized in that, said magnesium compound is selected from magnesium halide, oxyethyl group magnesium halide, magnesium ethylate and butoxy magnesium.
12. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-11; It is characterized in that said IVB family metallic compound is selected from one or more in halogenide, alkylate and the halogenated alkyl compounds of IVB family metal.
13. the preparation method according to aspect 12 described magnesium compound load type non-metallocene catalysts is characterized in that, said IVB family metallic compound is selected from IVB family metal halide.
14. the preparation method according to aspect 13 described magnesium compound load type non-metallocene catalysts is characterized in that, said IVB family metal halide is selected from titanium tetrachloride and zirconium tetrachloride.
15. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-14 is characterized in that, is 1: 0.1～100 in the said chemical processing agent of IVB family metallic element with mol ratio in the said magnesium compound of magnesium elements.
16. the preparation method according to aspect 15 described magnesium compound load type non-metallocene catalysts is characterized in that, is 1: 0.5～50 in the said chemical processing agent of IVB family metallic element with mol ratio in the said magnesium compound of magnesium elements.
17. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-16 is characterized in that, the mass ratio of said Nonmetallocene part and said product of contact is 0.01～0.50: 1.
18. the preparation method according to aspect 17 described magnesium compound load type non-metallocene catalysts is characterized in that, the mass ratio of said Nonmetallocene part and said product of contact is 0.10～0.30: 1.
19. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-18; It is characterized in that; Said alcohol is selected from one or more in Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol and the alicyclic ring alcohol, and the optional group that is selected from alkyl, halogen atom and alkoxyl group of wherein said alcohol replaces.
20. the preparation method according to aspect 19 described magnesium compound load type non-metallocene catalysts is characterized in that, said alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18).
21. the preparation method according to aspect 20 described magnesium compound load type non-metallocene catalysts is characterized in that, said Fatty Alcohol(C12-C14 and C12-C18) is selected from ethanol and butanols.
22. preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-21; It is characterized in that; In the said magnesium compound of magnesium elements and the mol ratio of THF is 1: 5～100, is 1: 0.5～20 in the said magnesium compound of magnesium elements and the mol ratio of said alcohol.
23, according to the preparation method of aspect 22 described magnesium compound load type non-metallocene catalysts; It is characterized in that; In the said magnesium compound of magnesium elements and the mol ratio of THF is 1: 10～30, is 1: 1～8 in the said magnesium compound of magnesium elements and the mol ratio of said alcohol.
24. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-23 is characterized in that, by volume, it is 1: 0.5～6 that said deposition is used the solvent and the ratio of THF.
25. the preparation method according to aspect 24 described magnesium compound load type non-metallocene catalysts is characterized in that, by volume, it is 1: 1～4 that said deposition is used the solvent and the ratio of THF.
26. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 4-25 is characterized in that, said deposition is selected from alkane with solvent.
27. the preparation method according to aspect 26 described magnesium compound load type non-metallocene catalysts is characterized in that, said deposition is selected from pentane, hexane, heptane and decane with solvent.
28. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 2-27 is characterized in that, the said chemical processing agent that helps is selected from MAO, isobutyl aluminium alkoxide, triethyl aluminum and the triisobutyl aluminium one or more.
29. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 2-27 is characterized in that, is 1: 0.5～8 in the said magnesium compound of magnesium elements with helping the mol ratio of chemical processing agent in aluminium element said.
30. the preparation method according to aspect 29 described magnesium compound load type non-metallocene catalysts is characterized in that, is 1: 1～4 in the said magnesium compound of magnesium elements with helping the mol ratio of chemical processing agent in aluminium element said.
31. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 1-30 is characterized in that, said Nonmetallocene part is selected from the compound with following structure:
Figure S2007101626760D00071
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure S2007101626760D00072
,-NR 23R 24,-N (O) R 25R 26, ,-PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39
B is selected from nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D is selected from Sauerstoffatom, sulphur atom, selenium atom, nitrogenous C 1-C 30Alkyl, phosphorated C 1-C 30Alkyl, sulfuryl, sulfoxide group,
Figure S2007101626760D00074
,-N (O) R 25R 26,
Figure S2007101626760D00075
Or-P (O) R 32(OR 33), wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
G is selected from C 1-C 30Alkyl, substituted C 1-C 30Alkyl or safing function property group;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R 1, R 2, R 3, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33And R 39Be selected from hydrogen, C independently of one another 1-C 30Alkyl, halogen atom, substituted C 1-C 30Alkyl or safing function property group, above-mentioned group can be the same or different to each other, and wherein adjacent group can become key or Cheng Huan each other.
32. the preparation method according to aspect 31 described magnesium compound load type non-metallocene catalysts is characterized in that,
Said Nonmetallocene part is selected from (A) with following structure and (B) compound:
Figure S2007101626760D00081
and
Figure S2007101626760D00082
Wherein F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
Other are according to aspect 31 said definition.
33. the preparation method according to aspect 32 described magnesium compound load type non-metallocene catalysts is characterized in that,
Said Nonmetallocene part is selected from the compound with following structure A-1 to A-4 and B-1 to B-4:
Figure S2007101626760D00083
Figure S2007101626760D00101
Wherein:
Y and Z are selected from nitrogen-containing group, oxy radical, sulfur-containing group independently of one another, contain seleno group or phosphorus-containing groups, and wherein N, O, S, Se and P are respectively ligating atom;
R 4, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20And R 21Be selected from hydrogen, C independently of one another 1-C 30Alkyl, halogen atom, substituted C 1-C 30Alkyl or safing function property group, above-mentioned group can be the same or different to each other, and wherein adjacent group can become key or Cheng Huan each other;
R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30Alkyl, substituted C 1-C 30Alkyl, oxy radical, sulfur-containing group, nitrogen-containing group or phosphorus-containing groups, prerequisite are to work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P, Se be respectively ligating atom;
Other are according to aspect 32 said definition.
34. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 31-33 is characterized in that,
Said halogen is selected from F, Cl, Br, I;
Said safing function property group is selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or contains tin group;
Said nitrogen-containing group is selected from ,-NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26
Said phosphorus-containing groups is selected from
Figure S2007101626760D00111
,-PR 28R 29,-P (O) R 30R 31Or-P (O) R 32(OR 33);
Said oxy radical be selected from hydroxyl ,-OR 34With-T-OR 34
Said sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The said seleno group that contains is selected from-SeR 38,-T-SeR 38,-Se (O) R 39Or-T-Se (O) R 39
Said group T is selected from C 1-C 30Alkyl, substituted C 1-C 30Alkyl or safing function property group;
Said C 1-C 30Alkyl is selected from C 1-C 30Alkyl, C 2-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;
Said substituted C 1-C 30Alkyl is selected from halogenated C 1-C 30Alkyl, halogenated C 6-C 30Aryl, halogenated C 8-C 30Condensed ring radical or halogenated C 4-C 30Heterocyclic radical;
Said silicon-containing group is selected from-SiR 42R 43R 44,-T-SiR 45
Said germanic group is selected from-GeR 46R 47R 48,-T-GeR 49
Saidly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54
Said R 34, R 35, R 36, R 37, R 38And R 42, R 43, R 44, R 45, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54Be selected from hydrogen, C independently of one another 1-C 30Alkyl, halogen atom, substituted C 1-C 30Alkyl or safing function property group.
35. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 31-34 is characterized in that,
Said Nonmetallocene part is selected from the compound with following structure:
Figure S2007101626760D00112
Figure S2007101626760D00121
and
Figure S2007101626760D00122
36. the preparation method according to aspect each described magnesium compound load type non-metallocene catalyst of 32-35 is characterized in that,
Said Nonmetallocene part is selected from the compound with following structure:
Figure S2007101626760D00123
and
Figure S2007101626760D00124
37. a magnesium compound load type non-metallocene catalyst comprises carrier and load non-metallocene catalyst on it, it is characterized in that, it is to make according to the preparation method of aspect 1～36 each described magnesium compound load type non-metallocene catalyst.
38. alkene homopolymerization/copolymerization process; It is characterized in that; Being Primary Catalysts according to aspect 37 described magnesium compound load type non-metallocene catalysts; To be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is promotor, makes alkene homopolymerization or copolymerization.
39., it is characterized in that said promotor is selected from one or more in aikyiaiurnirsoxan beta and the aluminum alkyls according to aspect 38 described alkene homopolymerization/copolymerization process.
40., it is characterized in that said promotor is selected from MAO and triethyl aluminum according to aspect 39 described alkene homopolymerization/copolymerization process.
41., it is characterized in that said alkene is selected from C according to each described alkene homopolymerization/copolymerization process of aspect 38-40 2～C 10Monoolefine, diolefin, cycloolefin and other ethylenically unsaturated compounds.
42., it is characterized in that said C according to aspect 41 described alkene homopolymerization/copolymerization process 2～C 10Monoolefine is selected from ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene and vinylbenzene; Said diolefin is selected from 1; 4-divinyl, 2,5-pentadiene, 1,6-hexadiene and 1; The 7-octadiene, and said other ethylenically unsaturated compounds are selected from vinyl acetate and (methyl) propenoate.
Preparing method's technology simple possible of magnesium compound load type non-metallocene catalyst of the present invention, and the charge capacity of Nonmetallocene part is adjustable, can improve its charge capacity significantly, improves the polymerization activity of this catalyzer thus significantly.
In addition, through adopting different chemical processing agent consumptions, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst adapts to different olefin polymerization requirement thus.
When employing load type non-metallocene catalyst that the present invention obtained and promotor constitute catalystsystem, only need fewer promotor (such as MAO or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity.
Embodiment
At first; The present invention relates to a kind of preparation method of magnesium compound load type non-metallocene catalyst; May further comprise the steps: magnesium compound is contacted with the chemical processing agent that is selected from IVB family metallic compound; Obtain the step of product of contact and handle said product of contact, obtain the step of said load type non-metallocene catalyst with the Nonmetallocene part.
Said magnesium compound is the carrier of this load type non-metallocene catalyst, such as being selected from magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium, alkyl alkoxy magnesium or its any one or multiple mixture.
Particularly, magnesium halide is such as being selected from magnesium chloride (MgCl 2), magnesium bromide (MgBr 2), magnesium iodide (MgI 2) and Sellaite (MgF 2) etc., wherein preferred magnesium chloride.
The alkoxyl group magnesium halide is such as being selected from methoxyl group chlorination magnesium (Mg (OCH 3) Cl), oxyethyl group magnesium chloride (Mg (OC 2H 5) Cl), propoxy-magnesium chloride (Mg (OC 3H 7) Cl), n-butoxy magnesium chloride (Mg (OC 4H 9) Cl), isobutoxy magnesium chloride (Mg (i-OC 4H 9) Cl), methoxyl group magnesium bromide (Mg (OCH 3) Br), oxyethyl group magnesium bromide (Mg (OC 2H 5) Br), propoxy-magnesium bromide (Mg (OC 3H 7) Br), n-butoxy magnesium bromide (Mg (OC 4H 9) Br), isobutoxy magnesium bromide (Mg (i-OC 4H 9) Br), methoxyl group magnesium iodide (Mg (OCH 3) I), oxyethyl group magnesium iodide (Mg (OC 2H 5) I), propoxy-magnesium iodide (Mg (OC 3H 7) I), n-butoxy magnesium iodide (Mg (OC 4H 9) I) and isobutoxy magnesium iodide (Mg (i-OC 4H 9) I) etc., wherein preferred methoxyl group chlorination magnesium, oxyethyl group magnesium chloride and isobutoxy magnesium chloride.
Alkoxyl magnesium is such as being selected from magnesium methylate (Mg (OCH 3) 2), magnesium ethylate (Mg (OC 2H 5) 2), propoxy-magnesium (Mg (OC 3H 7) 2), butoxy magnesium (Mg (OC 4H 9) 2), isobutoxy magnesium (Mg (i-OC 4H 9) 2) and 2-ethyl hexyl oxy magnesium (Mg (OCH 2CH (C 2H 5) C 4H) 2) etc., wherein preferred magnesium ethylate and isobutoxy magnesium.
Alkyl magnesium is such as being selected from methyl magnesium (Mg (CH 3) 2), magnesium ethide (Mg (C 2H 5) 2), propyl group magnesium (Mg (C 3H 7) 2), normal-butyl magnesium (Mg (C 4H 9) 2) and isobutyl-magnesium (Mg (i-C 4H 9) 2) etc., wherein preferred magnesium ethide and normal-butyl magnesium.
Alkyl halide magnesium is such as being selected from methylmagnesium-chloride (Mg (CH 3) Cl), ethylmagnesium chloride (Mg (C 2H 5) Cl), propyl group magnesium chloride (Mg (C 3H 7) Cl), normal-butyl chlorination magnesium (Mg (C 4H 9) Cl), isobutyl-chlorination magnesium (Mg (i-C 4H 9) Cl), methyl-magnesium-bromide (Mg (CH 3) Br), ethylmagnesium bromide (Mg (C 2H 5) Br), propyl group magnesium bromide (Mg (C 3H 7) Br), normal-butyl bromination magnesium (Mg (C 4H 9) Br), isobutyl-bromination magnesium (Mg (i-C 4H 9) Br), methyl magnesium iodide (Mg (CH 3) I), ethyl magnesium iodide (Mg (C 2H 5) I), propyl group magnesium iodide (Mg (C 3H 7) I), normal-butyl iodate magnesium (Mg (C 4H 9) I) and isobutyl-iodate magnesium (Mg (i-C 4H 9) I) etc., wherein preferable methyl magnesium chloride, ethylmagnesium chloride and isobutyl-chlorination magnesium.
Alkyl alkoxy magnesium is such as being selected from methyl methoxy base magnesium (Mg (OCH 3) (CH 3)), methyl ethoxy magnesium (Mg (OC 2H 5) (CH 3)), methyl propoxy-magnesium (Mg (OC 3H 7) (CH 3)), methyl n-butoxy magnesium (Mg (OC 4H 9) (CH 3)), methyl isobutoxy magnesium (Mg (i-OC 4H 9) (CH 3)), ethyl magnesium methylate (Mg (OCH 3) (C 2H 5)), ethyl magnesium ethylate (Mg (OC 2H 5) (C 2H 5)), ethyl propoxy-magnesium (Mg (OC 3H 7) (C 2H 5)), ethyl n-butoxy magnesium (Mg (OC 4H 9) (C 2H 5)), ethyl isobutoxy magnesium (Mg (i-OC 4H 9) (C 2H 5)), propyl group magnesium methylate (Mg (OCH 3) (C 3H 7)), propyl group magnesium ethylate (Mg (OC 2H 5) (C 3H 7)), propyl group propoxy-magnesium (Mg (OC 3H 7) (C 3H 7)), propyl group n-butoxy magnesium (Mg (OC 4H 9) (C 3H 7)), propyl group isobutoxy magnesium (Mg (i-OC 4H 9) (C 3H 7)), normal-butyl magnesium methylate (Mg (OCH 3) (C 4H 9)), normal-butyl magnesium ethylate (Mg (OC 2H 5) (C 4H 9)), normal-butyl propoxy-magnesium (Mg (OC 3H 7) (C 4H 9)), normal-butyl n-butoxy magnesium (Mg (OC 4H 9) (C 4H 9)), normal-butyl isobutoxy magnesium (Mg (i-OC 4H 9) (C 4H 9)), isobutyl-magnesium methylate (Mg (OCH 3) (i-C 4H 9)), isobutyl-magnesium ethylate (Mg (OC 2H 5) (i-C 4H 9)), isobutyl-propoxy-magnesium (Mg (OC 3H 7) (i-C 4H 9)), isobutyl-n-butoxy magnesium (Mg (OC 4H 9) (i-C 4H 9)) and isobutyl-isobutoxy magnesium (Mg (i-OC 4H 9) (i-C 4H 9)) etc., wherein preferred butyl magnesium ethylate.
These magnesium compounds can use a kind of separately, also can multiple mixing use, and do not have special restriction.For example, arbitrarily between the two mol ratio is such as being 0.25～4, and is preferred 0.5～3, more preferably 1～2.
In one embodiment, the magnesium compound that the present invention adopted can be its modified form.This modification magnesium compound is such as making it to precipitate with solvent and obtain through in by said magnesium compound and solution that THF-pure mixed solvent constitutes, adding deposition.After deposition,, can obtain this modification magnesium compound thus through solid-liquid separating methods such as filtrations.
Particularly, magnesium compound is joined in the THF, add alcohol then,, dissolve fully to magnesium compound, obtain magnesium compound solution 20 ℃ of TR internal heating stirrings to 5 ℃ of the boiling points that is lower than THF-pure mixed solvent.Add deposition then and make it deposition, filter at last, wash and dry thus obtained modification magnesium compound with solvent.
The dissolution time that the modification magnesium compound is prepared in the process does not have special qualification.Be known that when selecting temperature low, should adopt long dissolution time, and when selecting temperature higher, can adopt short dissolution time.For example, dissolution time was generally 0.5～24 hour.In this preparation process, can utilize to stir to promote dissolving and the deposition of magnesium compound in mixed solvent, and help the final deposition of magnesium compound with the dispersion of solvent in magnesium compound solution.This stirring can be adopted any form, and such as stirring rake etc., its rotating speed is generally 10～1000 rev/mins.
In the preparation method of this modification magnesium compound, said alcohol be such as can being selected from Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol and the alicyclic ring alcohol one or more, and said alcohol can choose the group that is selected from alkyl, halogen atom and alkoxyl group wantonly and replace, wherein preferred fat alcohol.For example, Fatty Alcohol(C12-C14 and C12-C18) is such as methyl alcohol, ethanol, propyl alcohol, 2-propyl alcohol, butanols, amylalcohol, 2-methyl amyl alcohol, 2-ethylpentanol, 2-hexyl butanols, hexanol and 2-Ethylhexyl Alcohol etc., wherein preferred alcohol, butanols and 2-Ethylhexyl Alcohol; Aromatic alcohol is such as phenylcarbinol, phenylethyl alcohol and methylbenzyl alcohol etc., wherein preferred phenylethyl alcohol; Cyclic alcohol is such as hexalin, cyclopentanol and ring octanol etc., wherein preferred hexalin; The substituted alcohol of alkyl is such as methylcyclopentanol, ethyl cyclopentanol, propyl group cyclopentanol, methyl-cyclohexanol, ethyl cyclohexanol, propyl group hexalin, methyl ring octanol, ethyl ring octanol and propyl group ring octanol etc., wherein preferable methyl hexalin; The substituted alcohol of halogen atom is such as trichlorine methyl alcohol, ethapon and three Mecorals etc., wherein preferred trichlorine methyl alcohol; The substituted alcohol of alkoxyl group is such as glycol-ether, terepthaloyl moietie-n-butyl ether and 1-butoxy-2-propyl alcohol etc., wherein preferred glycol-ether.In these alcohol, more preferably ethanol and butanols.
These alcohol can use a kind of separately, also can multiple mixing use.
When the said magnesium compound solution of preparation; Be generally 1: 5～100 in the said magnesium compound of magnesium elements and the mol ratio of THF; Preferred 1: 10～30, and be generally 1: 0.5～20 in the said magnesium compound of magnesium elements and the mol ratio of said alcohol, preferred 1: 1～8.
When preparing said modification magnesium compound, said deposition is used solvent to select for use anyly for said magnesium compound, to be poor solvent, and is the solvent of good solvent for said THF-pure mixed solvent, such as enumerating alkane solvents.
As said alkane solvents, can enumerate pentane, hexane, heptane, octane, nonane and decane etc., wherein preferred hexane, heptane and decane, most preferably hexane.
These depositions can be used a kind of separately with solvent, also can multiple mixing use.
Said deposition is not had special qualification with the consumption of solvent, but by volume, said deposition is generally 1: 0.5～6, preferred 1: 1～4 with the ratio of solvent and THF.
Also there is no particular limitation with the temperature of solvent to said precipitation, but general preferred normal temperature, and this precipitation process is generally also preferably carried out after magnesium compound solution is cooled to normal temperature.In addition, do not have special qualification for filtration, washing and the drying means of said modification magnesium compound (deposition), can be selected arbitrarily as required.
Magnesium compound of the present invention (comprising the modification magnesium compound) can directly be used for carrying out the contacting step with chemical processing agent; But one preferred embodiment in; With before chemical processing agent contacts, anticipate said magnesium compound (pre-treatment step) with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and its mixture.
Said aikyiaiurnirsoxan beta can be selected from the line style aikyiaiurnirsoxan beta R shown in the following general formula (I) 2-Al-(Al (R)-O) n-O-AlR 2And the ring-type aikyiaiurnirsoxan beta shown in the following general formula (II)-(Al (R)-O-) N+2
Figure S2007101626760D00161
Wherein, the R group can be same to each other or different to each other, and is preferably identical, and is independently from each other C 1-C 8Alkyl, preferable methyl, ethyl and isobutyl-, most preferable; N is the integer of 1-50, preferred 10～30.
Specifically for example, this aikyiaiurnirsoxan beta is preferably selected from MAO, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide, butyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide, wherein most preferable aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.
These aikyiaiurnirsoxan beta can be used a kind of separately, and perhaps combination is used multiple.
Said aluminum alkyls is for having the compound of following general formula (III):
Al(R) 3 (III)
Wherein the R group can be same to each other or different to each other, and is preferably identical, and is independently from each other C 1-C 8Alkyl, preferable methyl, ethyl and isobutyl-, most preferable.
Particularly, this aluminum alkyls is such as enumerating trimethylaluminium (Al (CH 3) 3), triethyl aluminum (Al (CH 3CH 2) 3), tri-propyl aluminum (Al (C 3H 7) 3), triisobutyl aluminium (Al (i-C 4H 9) 3), three n-butylaluminum (Al (C 4H 9) 3), triisopentyl aluminium (Al (i-C 5H 11) 3), three n-pentyl aluminium (Al (C 5H 11) 3), three hexyl aluminium (Al (C 6H 13) 3), three isohexyl aluminium (Al (i-C 6H 13) 3), diethylmethyl aluminium (Al (CH 3) (CH 3CH 2) 2) and dimethyl ethyl aluminium (Al (CH 3CH 2) (CH 3) 2) etc., wherein preferred trimethylaluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, most preferably triethyl aluminum and triisobutyl aluminium.
These aluminum alkylss can use a kind of separately, and perhaps combination is used multiple.
Based on the present invention, as the said chemical treatments that helps, can only adopt aikyiaiurnirsoxan beta, also can only adopt alkyl aluminum, also can adopt its one or more mixture separately.And, each components in proportions in this mixture there is not special qualification, can select arbitrarily as required.
When carrying out this pre-treatment given to this invention, be generally 1: 0.5～8, preferred 1: 1～4 in the said magnesium compound of magnesium elements and the said mol ratio of chemical processing agent that helps in aluminium element.
As the method for carrying out said pre-treatment step, can enumerate following method.At first prepare the said solution that helps chemical processing agent; The said chemical processing agent that helps that in normal temperature to solution, adds specified amount then under the temperature below the boiling point of solvent to magnesium compound; React 0.5～6 hour (in case of necessity by stirring), thereby obtain through this pretreated said magnesium compound.The pre-treatment magnesium compound that is obtained can be through filtering and washing (1～6 time; Preferred 1～3 time) mode from mixed solution, separate subsequent use (preferably finally through super-dry), but also can separate and directly be used for carrying out the contacting step with the chemical processing agent that is described below.
Said when helping the chemical treatment agent solution in preparation, employed solvent there is not special qualification, as long as it can dissolve this and help chemical processing agent.Particularly; Can enumerate alkane or halogenated alkane, C6～C12 aromatic hydrocarbons or the halogenated aryl hydrocarbon etc. of C5～C12; Such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecyl, hexanaphthene, toluene, ethylbenzene, YLENE, 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.
Should be noted in the discussion above that can not select for use this moment can the dissolved magnesium compound solvent, such as ether solvent, further such as THF etc.
These solvents can use a kind of separately, and perhaps combination is used multiple.
In addition, the said concentration of chemical processing agent in its solution that helps is not had special qualification, can suitably select as required, as long as can realize said magnesium compound given to this invention and the said molar ratio range that helps chemical processing agent.
As previously mentioned; Magnesium compound of the present invention (hereinafter; Said magnesium compound comprises magnesium compound itself and modification magnesium compound) can directly be used for carrying out the contacting step with chemical processing agent, but also can be used further to this contacting step through after the aforesaid pre-treatment step.
According to the present invention, said chemical processing agent is selected from IVB family metallic compound.As said IVB family metallic compound, can enumerate IVB family metal halide, IVB family metal alkyl compound, IVB family metal alkoxide compound, IVB family metal alkyl halides and IVB family metal alkoxide halogenide.
As said IVB family metal halide, alkylate, alkoxy compound, alkyl halide and alkoxy halide, can enumerate the compound of following general formula (IV) structure:
M(OR 1) mX nR 2 4-m-n (IV)
Wherein:
M is selected from 0,1,2,3,4;
N is selected from 0,1,2,3,4;
M is an IVB family metal, such as titanium, zirconium, hafnium etc.;
X is a halogen, such as F, Cl, Br, I etc.;
R 1And R 2Be selected from C independently of one another 1-C 30Alkyl is such as methyl, ethyl, propyl group, normal-butyl, isobutyl-etc., R 1And R 2Can be identical, also can be different.
Particularly, said IVB family metal halide can be enumerated titanium tetrafluoride (TiF 4), titanium tetrachloride (TiCl 4), titanium tetrabromide (TiBr 4), titanium tetra iodide (TiI 4);
Zirconium tetrafluoride (ZrF 4), zirconium tetrachloride (ZrCl 4), tetrabormated zirconium (ZrBr 4), zirconium tetraiodide (ZrI 4);
Tetrafluoride hafnium (HfF 4), hafnium tetrachloride (HfCl 4), hafnium (HfBr 4), tetraiodide hafnium (HfI 4);
Said IVB family metal alkyl compound can be enumerated tetramethyl-titanium (Ti (CH 3) 4), tetraethyl-titanium (Ti (CH 3CH 2) 4), four isobutyl-titanium (Ti (i-C 4H 9) 4), tetra-n-butyl titanium (Ti (C 4H 9) 4), triethyl methyltitanium (Ti (CH 3) (CH 3CH 2) 3), diethyl-dimethyl titanium (Ti (CH 3) 2(CH 3CH 2) 2), trimethylammonium ethyl titanium (Ti (CH 3) 3(CH 3CH 2)), triisobutyl methyltitanium (Ti (CH 3) (i-C 4H 9) 3), diisobutyl dimethyl-titanium (Ti (CH 3) 2(i-C 4H 9) 2), trimethylammonium isobutyl-titanium (Ti (CH 3) 3(i-C 4H 9)), triisobutyl ethyl titanium (Ti (CH 3CH 2) (i-C 4H 9) 3), diisobutyl diethylammonium 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 diethylammonium titanium (Ti (CH 3CH 2) 2(C 4H 9) 2), triethyl normal-butyl titanium (Ti (CH 3CH 2) 3(C 4H 9)) etc.;
Tetramethyl-zirconium (Zr (CH 3) 4), tetraethyl-zirconium (Zr (CH 3CH 2) 4), four isobutyl-zirconium (Zr (i-C 4H 9) 4), tetra-n-butyl zirconium (Zr (C 4H 9) 4), triethyl methylcyclopentadienyl zirconium (Zr (CH 3) (CH 3CH 2) 3), diethyl-dimethyl zirconium (Zr (CH 3) 2(CH 3CH 2) 2), trimethylammonium ethyl zirconium (Zr (CH 3) 3(CH 3CH 2)), triisobutyl methylcyclopentadienyl zirconium (Zr (CH 3) (i-C 4H 9) 3), diisobutyl zirconium dimethyl (Zr (CH 3) 2(i-C 4H 9) 2), trimethylammonium isobutyl-zirconium (Zr (CH 3) 3(i-C 4H 9)), triisobutyl ethyl zirconium (Zr (CH 3CH 2) (i-C 4H 9) 3), diisobutyl diethylammonium 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 diethylammonium zirconium (Zr (CH 3CH 2) 2(C 4H 9) 2), triethyl normal-butyl zirconium (Zr (CH 3CH 2) 3(C 4H 9)) etc.;
Tetramethyl-hafnium (Hf (CH 3) 4), tetraethyl-hafnium (Hf (CH 3CH 2) 4), four isobutyl-hafnium (Hf (i-C 4H 9) 4), tetra-n-butyl hafnium (Hf (C 4H 9) 4), triethyl methylcyclopentadienyl hafnium (Hf (CH 3) (CH 3CH 2) 3), diethyl-dimethyl hafnium (Hf (CH 3) 2(CH 3CH 2) 2), trimethylammonium ethyl hafnium (Hf (CH 3) 3(CH 3CH 2)), triisobutyl methylcyclopentadienyl hafnium (Hf (CH 3) (i-C 4H 9) 3), diisobutyl dimethyl-hafnium (Hf (CH 3) 2(i-C 4H 9) 2), trimethylammonium isobutyl-hafnium (Hf (CH 3) 3(i-C 4H 9)), triisobutyl ethyl hafnium (Hf (CH 3CH 2) (i-C 4H 9) 3), diisobutyl diethylammonium 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 diethylammonium hafnium (Hf (CH 3CH 2) 2(C 4H 9) 2), triethyl normal-butyl hafnium (Hf (CH 3CH 2) 3(C 4H 9)) etc.;
Said IVB family metal alkoxide compound can be enumerated tetramethoxy titanium (Ti (OCH 3) 4), purity titanium tetraethoxide (Ti (OCH 3CH 2) 4), four isobutoxy titanium (Ti (i-OC 4H 9) 4), four titanium n-butoxide (Ti (OC 4H 9) 4), triethoxy methoxyl group titanium (Ti (OCH 3) (OCH 3CH 2) 3), diethoxy dimethoxy titanium (Ti (OCH 3) 2(OCH 3CH 2) 2), trimethoxy ethanolato-titanium (Ti (OCH 3) 3(OCH 3CH 2)), three isobutoxy methoxyl group titanium (Ti (OCH 3) (i-OC 4H 9) 3), two isobutoxy dimethoxy titanium (Ti (OCH 3) 2(i-OC 4H 9) 2), trimethoxy isobutoxy titanium (Ti (OCH 3) 3(i-OC 4H 9)), three isobutoxy ethanolato-titanium (Ti (OCH 3CH 2) (i-OC 4H 9) 3), two isobutoxy diethoxy titanium (Ti (OCH 3CH 2) 2(i-OC 4H 9) 2), triethoxy isobutoxy titanium (Ti (OCH 3CH 2) 3(i-OC 4H 9)), three n-butoxy methoxyl group titanium (Ti (OCH 3) (OC 4H 9) 3), two n-butoxy dimethoxy titanium (Ti (OCH 3) 2(OC 4H 9) 2), trimethoxy titanium n-butoxide (Ti (OCH 3) 3(OC 4H 9)), three n-butoxy methoxyl group titanium (Ti (OCH 3CH 2) (OC 4H 9) 3), two n-butoxy diethoxy titanium (Ti (OCH 3CH 2) 2(OC 4H 9) 2), triethoxy titanium n-butoxide (Ti (OCH 3CH 2) 3(OC 4H 9)) etc.;
Tetramethoxy zirconium (Zr (OCH 3) 4), tetraethoxy zirconium (Zr (OCH 3CH 2) 4), four isobutoxy zirconium (Zr (i-OC 4H 9) 4), four n-butoxy zirconium (Zr (OC 4H 9) 4), triethoxy methoxyl group zirconium (Zr (OCH 3) (OCH 3CH 2) 3), diethoxy dimethoxy zirconium (Zr (OCH 3) 2(OCH 3CH 2) 2), trimethoxy oxyethyl group zirconium (Zr (OCH 3) 3(OCH 3CH 2)), three isobutoxy methoxyl group zirconium (Zr (OCH 3) (i-OC 4H 9) 3), two isobutoxy dimethoxy zirconium (Zr (OCH 3) 2(i-OC 4H 9) 2), trimethoxy isobutoxy zirconium (Zr (OCH 3) 3(i-C 4H 9)), three isobutoxy oxyethyl group zirconium (Zr (OCH 3CH 2) (i-OC 4H 9) 3), two isobutoxy diethoxy zirconium (Zr (OCH 3CH 2) 2(i-OC 4H 9) 2), triethoxy isobutoxy zirconium (Zr (OCH 3CH 2) 3(i-OC 4H 9)), three n-butoxy methoxyl group zirconium (Zr (OCH 3) (OC 4H 9) 3), two n-butoxy dimethoxy zirconium (Zr (OCH 3) 2(OC 4H 9) 2), trimethoxy n-butoxy zirconium (Zr (OCH 3) 3(OC 4H 9)), three n-butoxy methoxyl group zirconium (Zr (OCH 3CH 2) (OC 4H 9) 3), two n-butoxy diethoxy zirconium (Zr (OCH 3CH 2) 2(OC 4H 9) 2), triethoxy n-butoxy zirconium (Zr (OCH 3CH 2) 3(OC 4H 9)) etc.;
Tetramethoxy hafnium (Hf (OCH 3) 4), tetraethoxy hafnium (HF (OCH 3CH 2) 4), four isobutoxy hafnium (Hf (i-OC 4H 9) 4), four n-butoxy hafnium (Hf (OC 4H 9) 4), triethoxy methoxyl group hafnium (Hf (OCH 3) (OCH 3CH 2) 3), diethoxy dimethoxy hafnium (Hf (OCH 3) 2(OCH 3CH 2) 2), trimethoxy oxyethyl group hafnium (Hf (OCH 3) 3(OCH 3CH 2)), three isobutoxy methoxyl group hafnium (Hf (OCH 3) (i-OC 4H 9) 3), two isobutoxy dimethoxy hafnium (Hf (OCH 3) 2(i-OC 4H 9) 2), trimethoxy isobutoxy hafnium (Hf (OCH 3) 3(i-OC 4H 9)), three isobutoxy oxyethyl group hafnium (Hf (OCH 3CH 2) (i-OC 4H 9) 3), two isobutoxy diethoxy hafnium (Hf (OCH 3CH 2) 2(i-OC 4H 9) 2), triethoxy isobutoxy hafnium (Hf (OCH 3CH 2) 3(i-C 4H 9)), three n-butoxy methoxyl group hafnium (Hf (OCH 3) (OC 4H 9) 3), two n-butoxy dimethoxy hafnium (Hf (OCH 3) 2(OC 4H 9) 2), trimethoxy n-butoxy hafnium (Hf (OCH 3) 3(OC 4H 9)), three n-butoxy methoxyl group hafnium (Hf (OCH 3CH 2) (OC 4H 9) 3), two n-butoxy diethoxy hafnium (Hf (OCH 3CH 2) 2(OC 4H 9) 2), triethoxy n-butoxy hafnium (Hf (OCH 3CH 2) 3(OC 4H 9)) etc.
Said IVB family metal alkyl halides can be enumerated trimethylammonium titanium chloride (TiCl (CH 3) 3), triethyl titanium chloride (TiCl (CH 3CH 2) 3), triisobutyl titanium chloride (TiCl (i-C 4H 9) 3), three normal-butyl chlorination titanium (TiCl (C 4H 9) 3), dimethyl-titanium dichloride (TiCl 2(CH 3) 2), diethylammonium titanium dichloride (TiCl 2(CH 3CH 2) 2), diisobutyl titanium dichloride (TiCl 2(i-C 4H 9) 2), three normal-butyl chlorination titanium (TiCl (C 4H 9) 3), methyl titanous chloride (Ti (CH 3) Cl 3), ethyl titanous chloride (Ti (CH 3CH 2) Cl 3), isobutyl-titanous chloride (Ti (i-C 4H 9) Cl 3), normal-butyl titanous chloride (Ti (C 4H 9) Cl 3);
Trimethylammonium titanium bromide (TiBr (CH 3) 3), triethyl titanium bromide (TiBr (CH 3CH 2) 3), triisobutyl titanium bromide (TiBr (i-C 4H 9) 3), three normal-butyl bromination titanium (TiBr (C 4H 9) 3), dimethyl-dibrominated titanium (TiBr 2(CH 3) 2), diethylammonium dibrominated titanium (TiBr 2(CH 3CH 2) 2), diisobutyl dibrominated titanium (TiBr 2(i-C 4H 9) 2), three normal-butyl bromination titanium (TiBr (C 4H 9) 3), methyl titanium tribromide (Ti (CH 3) Br 3), ethyl titanium tribromide (Ti (CH 3CH 2) Br 3), isobutyl-titanium tribromide (Ti (i-C 4H 9) Br 3), normal-butyl titanium tribromide (Ti (C 4H 9) Br 3);
Trimethylammonium zirconium chloride (ZrCl (CH 3) 3), triethyl zirconium chloride (ZrCl (CH 3CH 2) 3), triisobutyl zirconium chloride (ZrCl (i-C 4H 9) 3), three normal-butyl chlorination zirconium (ZrCl (C 4H 9) 3), dimethyl-zirconium dichloride (ZrCl 2(CH 3) 2), diethylammonium zirconium dichloride (ZrCl 2(CH 3CH 2) 2), diisobutyl zirconium dichloride (ZrCl 2(i-C 4H 9) 2), three normal-butyl chlorination zirconium (ZrCl (C 4H 9) 3), methyl tri-chlorination zirconium (Zr (CH 3) Cl 3), ethyl tri-chlorination zirconium (Zr (CH 3CH 2) Cl 3), isobutyl-tri-chlorination zirconium (Zr (i-C 4H 9) Cl 3), normal-butyl tri-chlorination zirconium (Zr (C 4H 9) Cl 3);
Trimethylammonium zirconium bromide (ZrBr (CH 3) 3), triethyl zirconium bromide (ZrBr (CH 3CH 2) 3), triisobutyl zirconium bromide (ZrBr (i-C 4H 9) 3), three normal-butyl bromination zirconium (ZrBr (C 4H 9) 3), dimethyl-dibrominated zirconium (ZrBr 2(CH 3) 2), diethylammonium dibrominated zirconium (ZrBr 2(CH 3CH 2) 2), diisobutyl dibrominated zirconium (ZrBr 2(i-C 4H 9) 2), three normal-butyl bromination zirconium (ZrBr (C 4H 9) 3), methyl tribromide zirconium (Zr (CH 3) Br 3), ethyl tribromide zirconium (Zr (CH 3CH 2) Br 3), isobutyl-tribromide zirconium (Zr (i-C 4H 9) Br 3), normal-butyl tribromide zirconium (Zr (C 4H 9) Br 3);
Trimethylammonium hafnium chloride (HfCl (CH 3) 3), triethyl hafnium chloride (HfCl (CH 3CH 2) 3), triisobutyl hafnium chloride (HfCl (i-C 4H 9) 3), three normal-butyl chlorination hafnium (HfCl (C 4H 9) 3), dimethyl-hafnium dichloride (HfCl 2(CH 3) 2), diethylammonium hafnium dichloride (HfCl 2(CH 3CH 2) 2), diisobutyl hafnium dichloride (HfCl 2(i-C 4H 9) 2), three normal-butyl chlorination hafnium (HfCl (C 4H 9) 3), methyl tri-chlorination hafnium (Hf (CH 3) Cl 3), ethyl tri-chlorination hafnium (Hf (CH 3CH 2) Cl 3), isobutyl-tri-chlorination hafnium (Hf (i-C 4H 9) Cl 3), normal-butyl tri-chlorination hafnium (Hf (C 4H 9) Cl 3);
Trimethylammonium bromination hafnium (HfBr (CH 3) 3), triethyl bromination hafnium (HfBr (CH 3CH 2) 3), triisobutyl bromination hafnium (HfBr (i-C 4H 9) 3), three normal-butyl bromination hafnium (HfBr (C 4H 9) 3), dimethyl-dibrominated hafnium (HfBr 2(CH 3) 2), diethylammonium 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);
Said IVB family metal alkoxide halogenide can be enumerated trimethoxy titanium chloride (TiCl (OCH 3) 3), triethoxy titanium chloride (TiCl (OCH 3CH 2) 3), three isobutoxy titanium chloride (TiCl (i-OC 4H 9) 3), three n-butoxy titanium chloride (TiCl (OC 4H 9) 3), dimethoxy titanium dichloride (TiCl 2(OCH 3) 2), diethoxy titanium dichloride (TiCl 2(OCH 3CH 2) 2), two isobutoxy titanium dichloride (TiCl 2(i-OC 4H 9) 2), three n-butoxy titanium chloride (TiCl (OC 4H 9) 3), methoxyl group titanous chloride (Ti (OCH 3) Cl 3), oxyethyl group titanous chloride (Ti (OCH 3CH 2) Cl 3), isobutoxy titanous chloride (Ti (i-C 4H 9) Cl 3), n-butoxy titanous chloride (Ti (OC 4H 9) Cl 3);
Trimethoxy titanium bromide (TiBr (OCH 3) 3), triethoxy titanium bromide (TiBr (OCH 3CH 2) 3), three isobutoxy titanium bromide (TiBr (i-OC 4H 9) 3), three n-butoxy titanium bromide (TiBr (OC 4H 9) 3), dimethoxy dibrominated titanium (TiBr 2(OCH 3) 2), diethoxy dibrominated titanium (TiBr 2(OCH 3CH 2) 2), two isobutoxy dibrominated titanium (TiBr 2(i-OC 4H 9) 2), three n-butoxy titanium bromide (TiBr (OC 4H 9) 3), methoxyl group titanium tribromide (Ti (OCH 3) Br 3), oxyethyl group titanium tribromide (Ti (OCH 3CH 2) Br 3), isobutoxy titanium tribromide (Ti (i-C 4H 9) Br 3), n-butoxy titanium tribromide (Ti (OC 4H 9) Br 3);
Trimethoxy zirconium chloride (ZrCl (OCH 3) 3), triethoxy zirconium chloride (ZrCl (OCH 3CH 2) 3), three isobutoxy zirconium chloride (ZrCl (i-OC 4H 9) 3), three n-butoxy zirconium chloride (ZrCl (OC 4H 9) 3), dimethoxy zirconium dichloride (ZrCl 2(OCH 3) 2), diethoxy zirconium dichloride (ZrCl 2(OCH 3CH 2) 2), two isobutoxy zirconium dichloride (ZrCl 2(i-OC 4H 9) 2), three n-butoxy zirconium chloride (ZrCl (OC 4H 9) 3), methoxyl group tri-chlorination zirconium (Zr (OCH 3) Cl 3), oxyethyl group tri-chlorination zirconium (Zr (OCH 3CH 2) Cl 3), isobutoxy tri-chlorination zirconium (Zr (i-C 4H 9) Cl 3), n-butoxy tri-chlorination zirconium (Zr (OC 4H 9) Cl 3);
Trimethoxy zirconium bromide (ZrBr (OCH 3) 3), triethoxy zirconium bromide (ZrBr (OCH 3CH 2) 3), three isobutoxy zirconium bromide (ZrBr (i-OC 4H 9) 3), three n-butoxy zirconium bromide (ZrBr (OC 4H 9) 3), dimethoxy dibrominated zirconium (ZrBr 2(OCH 3) 2), diethoxy dibrominated zirconium (ZrBr 2(OCH 3CH 2) 2), two isobutoxy dibrominated zirconium (ZrBr 2(i-OC 4H 9) 2), three n-butoxy zirconium bromide (ZrBr (OC 4H 9) 3), methoxyl group tribromide zirconium (Zr (OCH 3) Br 3), oxyethyl group tribromide zirconium (Zr (OCH 3CH 2) Br 3), isobutoxy tribromide zirconium (Zr (i-C 4H 9) Br 3), n-butoxy tribromide zirconium (Zr (OC 4H 9) Br 3);
Trimethoxy hafnium chloride (HfCl (OCH 3) 3), triethoxy hafnium chloride (HfCl (OCH 3CH 2) 3), three isobutoxy hafnium chloride (HfCl (i-OC 4H 9) 3), three n-butoxy hafnium chloride (HfCl (OC 4H 9) 3), dimethoxy hafnium dichloride (HfCl 2(OCH 3) 2), diethoxy hafnium dichloride (HfCl 2(OCH 3CH 2) 2), two isobutoxy hafnium dichloride (HfCl 2(i-OC 4H 9) 2), three n-butoxy hafnium chloride (HfCl (OC 4H 9) 3), methoxyl group tri-chlorination hafnium (Hf (OCH 3) Cl 3), oxyethyl group tri-chlorination hafnium (Hf (OCH 3CH 2) Cl 3), isobutoxy tri-chlorination hafnium (Hf (i-C 4H 9) Cl 3), n-butoxy tri-chlorination hafnium (Hf (OC 4H 9) Cl 3);
Trimethoxy bromination hafnium (HfBr (OCH 3) 3), triethoxy bromination hafnium (HfBr (OCH 3CH 2) 3), three isobutoxy bromination hafnium (HfBr (i-OC 4H 9) 3), three n-butoxy bromination hafnium (HfBr (OC 4H 9) 3), dimethoxy dibrominated hafnium (HfBr 2(OCH 3) 2), diethoxy dibrominated hafnium (HfBr 2(OCH 3CH 2) 2), two isobutoxy dibrominated hafnium (HfBr 2(i-OC 4H 9) 2), three n-butoxy bromination hafnium (HfBr (OC 4H 9) 3), methoxyl group tribromide hafnium (Hf (OCH 3) Br 3), oxyethyl group tribromide hafnium (Hf (OCH 3CH 2) Br 3), isobutoxy tribromide hafnium (Hf (i-C 4H 9) Br 3), n-butoxy tribromide hafnium (Hf (OC 4H 9) Br 3).
Wherein, as said IVB family metallic compound, preferred IVB family metal halide, more preferably TiCl 4, TiBr 4, ZrCl 4, ZrBr 4, HfCl 4, HfBr 4, TiCl most preferably 4And ZrCl 4
These IVB family metallic compounds can use a kind of separately, perhaps are used in combination multiple.
As the method for carrying out said contacting step; Obtain product of contact with contacting of said chemical processing agent as long as can realize said magnesium compound (comprising magnesium compound itself, modification magnesium compound and the pretreated magnesium compound of process); Do not have special qualification; Can enumerate following method, but be not limited to this.
Under the situation that adopts solid chemical processing agent (such as zirconium tetrachloride), at first prepare the solution of said chemical processing agent, add the said chemical processing agent of (the preferred dropping) specified amount then to magnesium compound; Under the situation that adopts liquid chemical treatment agent (such as titanium tetrachloride); Can be directly (but also can after being prepared into solution) the said chemical processing agent of specified amount is added (the preferred dropping) in magnesium compound, make contact reacts (in case of necessity by stirring) carry out preferred 1～8 hour 0.5～24 hour; More preferably 2～6 hours; Filter then and wash, then dry, obtain product of contact thus.
Said filtration, washing and drying can adopt ordinary method to carry out, and wherein washer solvent can adopt used identical solvent when dissolving solid chemical processing agent.This washing is generally carried out 1～8 time, and preferred 2～6 times, most preferably 2～4 times.
When carrying out said contacting step, be 1: 0.1～100 in the said chemical processing agent of IVB family metallic element with mol ratio in the said magnesium compound of magnesium elements, preferred 1: 0.5～50.
When the solution of the said chemical processing agent of preparation, employed solvent there is not special qualification, can be suitable for preparation used those when helping the chemical treatment agent solution.And these solvents can use a kind of separately, and perhaps combination is used multiple.
Should be noted in the discussion above that can not select for use this moment can the dissolved magnesium compound solvent, such as ether solvent, further such as THF etc.
The concentration of said chemical processing agent in its solution is not had special qualification, can suitably select as required, as long as can realize the molar ratio range of said magnesium compound given to this invention and said chemical processing agent.
According to the present invention, said catalytic temperature there is not special qualification yet.Though select for use higher temperature of reaction to help the reaction of chemical processing agent and magnesium compound carrier, can reduce the reaction times.But because solvent is different, its boiling point also is different.Those skilled in the art know that the temperature of reaction of chemical processing agent and carrier should be lower than the boiling point of solvent, and such as for hexane, temperature of reaction can be chosen between 20 ℃～65 ℃, can be chosen between 20 ℃～105 ℃ or the like for toluene.Therefore, temperature of reaction is different with the difference of solvent, cannot treat different things as the same, and is lower than between 5～10 ℃ of the solvent boiling points but be typically chosen in, but the lower limit of temperature is not limited.In addition, this catalytic time is had no particular limits, generally can select for use 0.5～24 hour.Under the situation that improves temperature of reaction, the reaction times can be suitably short more.
It is pointed out that in this contacting step, the use of solvent is not essential.Just be or, the reaction of said chemical processing agent and said magnesium compound can be carried out under the situation that does not have solvent to exist, but this moment, chemical processing agent was necessary for liquid state.Temperature of reaction and the reaction times of this moment can be suitably definite as required, and generally speaking, temperature of reaction should be lower than 5～10 ℃ of the boiling points of chemical processing agent at least, and the contact reacts time was generally 2～24 hours.For example, the reaction of chemical processing agent and carrier is fiercer, and temperature of reaction just is provided with lowly more, makes the reaction times long more thus.Such as, when chemical processing agent was titanium tetrachloride, temperature of reaction can be-30 ℃～126 ℃, the corresponding reaction times is 2～12 hours.
In addition, also can use obtained in the aforementioned pre-treatment step replace said magnesium compound to carry out this contacting step without crossing separated mixture.At this moment, owing to had solvent in this mixed solution, can omit the consumption that uses solvent or reduce solvent.
According to the present invention, the product of contact that is obtained can obtain magnesium compound load type non-metallocene catalyst of the present invention through handling with the Nonmetallocene part.
Said Nonmetallocene part is selected from the compound with following structure:
In a more concrete embodiment, said Nonmetallocene part is selected from (A) with following structure and (B) compound:
Figure S2007101626760D00261
and
Figure S2007101626760D00262
In a more concrete embodiment, said Nonmetallocene part is selected from the compound with following structure A-1 to A-4 and B-1 to B-4:
Figure S2007101626760D00263
Figure S2007101626760D00281
In above all structural formulas,
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure S2007101626760D00282
,-NR 23R 24,-N (O) R 25R 26,
Figure S2007101626760D00283
,-PR 28R 29,-P (O) R 30O 31, sulfuryl, sulfoxide group or-Se (O) R 39
B is selected from nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D is selected from Sauerstoffatom, sulphur atom, selenium atom, nitrogenous C 1-C 30Alkyl, phosphorated C 1-C 30Alkyl, sulfuryl, sulfoxide group, ,-N (O) R 25R 26,
Figure S2007101626760D00285
,-P (O) R 32(OR 33),
Wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
F is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
G is selected from C 1-C 30Alkyl, substituted C 1-C 30Alkyl or safing function property group;
Y and Z are selected from nitrogen-containing group, oxy radical, sulfur-containing group independently of one another, contain seleno group or phosphorus-containing groups, such as enumerating-NR 23R 24,-N (O) R 25R 26,-PR 28R 29,-P (O) R 30R 31,-OR 34,-SR 35,-S (O) R 36,-SeR 38With-Se (O) R 39, wherein N, O, S, Se and P are respectively ligating atom;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R 1, R 2, R 3, R 4, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, R 20, R 21, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33, R 34, R 35, R 36, R 38And R 39Be selected from hydrogen, C independently of one another 1-C 30Alkyl, halogen atom, substituted C 1-C 30Alkyl (wherein preferred halo alkyl, such as-CH 2Cl and-CH 2CH 2Cl) or safing function property group, above-mentioned group can be the same or different to each other, wherein adjacent group such as R 1With R 2, R 3, R 3With R 4, R 6, R 7, R 8, R 9, and R 23With R 24Or R 25With R 26Deng becoming key or Cheng Huan each other;
R 5Be selected from lone-pair electron on the nitrogen, hydrogen, C 1-C 30Alkyl, substituted C 1-C 30Alkyl, oxy radical (comprise hydroxyl and alkoxyl group, such as-OR 34With-T-OR 34), sulfur-containing group (comprises-SR 35,-T-S 35), nitrogen-containing group (comprises-NR 23R 24,-T-NR 23R 24), or phosphorus-containing groups (comprises-PR 28R 29,-T-PR 28R 29,-T-P (O) R 30R 31); Work as R 5For oxy radical, sulfur-containing group, nitrogen-containing group, when containing seleno group or phosphorus-containing groups, R 5In N, O, S, P, Se be respectively ligating atom, and can carry out coordination with IVB family atoms metal; With
According to the present invention, said halogen is selected from F, Cl, Br, I;
Said nitrogen-containing group is selected from ,-NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26
Phosphorus-containing groups is selected from
Figure S2007101626760D00292
,-PR 28R 29,-P (O) R 30R 31Or-P (O) R 32(OR 33);
Said oxy radical is selected from hydroxyl and alkoxyl group, such as-OR 34With-T-OR 34
Said sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The said seleno group that contains is selected from-SeR 38,-T-SeR 38,-Se (O) R 39Or-T-Se (O) R 39
Said group T is selected from C 1-C 30Alkyl, substituted C 1-C 30Alkyl or safing function property group;
Said R 37Be selected from hydrogen, C 1-C 30Alkyl, halogen atom, substituted C 1-C 30Alkyl or safing function property group.
According to the present invention, said C 1-C 30Alkyl comprises C 1-C 30Alkyl, C 2-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;
Said substituted C 1-C 30Alkyl refers to the alkyl that has one or more inert substituents.So-called inertia, the coordination process that refers to these substituting groups pair and central metal atom does not have substantial interference.Like non-specified otherwise, said substituted C 1-C 30Alkyl generally refers to halogenated C 1-C 30Alkyl, halogenated C 6-C 30Aryl, halogenated C 8-C 30Condensed ring radical or halogenated C 4-C 30Heterocyclic radical;
Safing function property group refers to except that alkyl and other safing function base the substituted alkyl.According to the present invention, described safing function property group be such as enumerating halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or containing tin group, particularly, and such as enumerating ether (like-O 34Or-TOR 35), C 1-C 10Ester group, C 1-C 10Amine, C 1-C 10Alkoxyl group and nitro etc.
Said silicon-containing group is selected from-SiR 42R 43R 44,-T-SiR 45
Said germanic group is selected from-GeR 46R 47R 48,-T-GeR 49
Saidly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54
Said R 42, R 43, R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54Be selected from hydrogen, C independently of one another 1-C 30Alkyl, halogen atom, substituted C 1-C 30Alkyl or safing function property group.
According to the present invention, said safing function property group will satisfy following condition:
(1) do not disturb coordination process with IVB family atoms metal,
(2) with structural formula in group A, D, E, F, Y and Z all different and
(3) coordination ability with IVB family atoms metal is lower than said A, D, E, F, Y and Z group, and does not replace the coordination of these groups and IVB family atoms metal.
As this Nonmetallocene part, such as enumerating compound with following structure:
Figure S2007101626760D00301
Figure S2007101626760D00311
Figure S2007101626760D00321
Figure S2007101626760D00331
Wherein, said Nonmetallocene part is preferably selected from the compound with following structure:
Figure S2007101626760D00342
Figure S2007101626760D00351
Wherein, said Nonmetallocene part also is preferably selected from the compound with following structure:
Figure S2007101626760D00352
Figure S2007101626760D00353
and
Figure S2007101626760D00354
Said Nonmetallocene part more preferably is selected from the compound with following structure:
Figure S2007101626760D00361
and
Figure S2007101626760D00362
These Nonmetallocene parts can use a kind of separately, and perhaps combination is used multiple.
According to the present invention; Through the product of contact that is obtained in the contacting step before handling with said Nonmetallocene part; IVB family metal contained in said Nonmetallocene part and this product of contact is reacted; Thereby original position generates Nonmetallocene title complex (original position load reaction), obtains magnesium compound load type non-metallocene catalyst of the present invention thus.
The qualification that the mode of carrying out of this original position load reaction is had no is as long as can realize this original position load reaction.Particularly, can enumerate following method.
The solution that at first prepares said Nonmetallocene part.If what select is that solubleness to said Nonmetallocene part is not very high solvent, the mode that then can select suitably heating is to promote its dissolving; And, then can not adopt type of heating for to the higher solvent of Nonmetallocene part solubleness.Stir if desired, the rotating speed that then should stir is at 10～500 rev/mins.According to the present invention to the regulation of non-metallocene catalyst content in the final load type non-metallocene catalyst; And the solvent that adopts of this stage is to the solvability of this Nonmetallocene part; The mass concentration of this Nonmetallocene part is generally 10～250 grams per liters in the solution, preferred 50～160 grams per liters.
To this moment used solvent do not have special qualification, as long as can dissolve said Nonmetallocene part, such as being selected from:
Alkane is such as pentane, hexane, heptane, octane, nonane, decane etc.;
Naphthenic hydrocarbon, such as hexanaphthene, pentamethylene, suberane, cyclodecane, cyclononane etc.;
Halogenated alkane is such as methylene dichloride, dichloro hexane, two chloroheptanes, trichloromethane, trichloroethane, three chlorobutanes, methylene bromide, ethylene dibromide, dibromo-heptane, methenyl bromide, tribromoethane, three NBBs etc.;
Halo naphthenic hydrocarbon, such as chlorocyclopentane, chlorocyclohexane, chloro suberane, chloro cyclooctane, chloro cyclononane, chloro cyclodecane, bromocyclopentane, bromocyclohexane, bromo suberane, bromo cyclooctane, bromo cyclononane, bromo cyclodecane,
Aromatic hydrocarbon is such as toluene, YLENE, trimethylbenzene, ethylbenzene, diethylbenzene etc.; With
Halogenated aromatic is such as chlorotoluene, chloro ethylbenzene, bromo toluene, bromo ethylbenzene etc.
Wherein, preferred alkane, halogenated alkane or aromatic hydrocarbon, most preferably hexane, methylene dichloride and toluene.
These solvents can use a kind of separately, and perhaps combination is used multiple.
Should be noted in the discussion above that can not select for use this moment can the dissolved magnesium compound solvent, such as ether solvent, further such as THF etc.
Then; Under evenly stirring, said product of contact is joined in this Nonmetallocene ligand solution in the TR that is lower than 5 ℃ of solvent boiling points in room temperature; So that the mass ratio of said Nonmetallocene part and said product of contact is 0.01～0.50: 1; Preferred 0.10～0.30: 1, continue reaction 0.5～24 hour.Stirring can be adopted modes such as helical-ribbon type stirring or the stirring of anchor formula, stirs for helical-ribbon type, and stirring velocity is generally 5～50 rev/mins, stirs for the anchor formula, and stirring velocity is generally 5～200 rev/mins.
After the reaction, with reaction mixture through filtration, washing and dry, perhaps without filtration and washing and convection drying promptly obtains magnesium compound load type non-metallocene catalyst of the present invention.Generally speaking, for the lower reaction mixture of solid content, a kind of mode before the employing, and, then adopt a kind of mode in back for the higher reaction mixture of solid content.In case of necessity, this washing is generally carried out 1～8 time, and preferred 2～6 times, most preferably 2～4 times.Said drying can adopt well-established law to carry out, and is dry such as rare gas element, vacuumize drying, and perhaps heating vacuumizes drying, preferably vacuumizes drying.Generally speaking, be generally 2～24 hours time of drying, but actual can be through sampling, and thermal weight loss situation is per sample judged dry terminal point.That is thermal weight loss is dry terminal point less than 5% under the temperature that the boiling point of the solvent that, adopts being lower than is 5～45 ℃.When selecting lower boiling solvent, can adopt short time of drying, select high boiling solvent then generally to adopt long time of drying.Drying temperature generally is lower than 5～45 ℃ of the boiling points of used solvent; Such as when adopting THF as solvent, drying temperature can be chosen between 23～63 ℃, when selecting toluene as solvent; Drying temperature can be chosen between 65～105 ℃; When selecting methylene dichloride as solvent, drying temperature can be chosen between 0～37 ℃ for another example, or the like.
In addition, consider the interaction between said product of contact and the Nonmetallocene part, reacted mixed solution generally carries out 0.5～24 hour airtight wearing out at normal temperatures, to increase the bond strength between carrier and the Nonmetallocene part.
Those skilled in the art knows that above-described various contacts and treating processes are generally all carried out under the anhydrous and oxygen-free condition of strictness, said here anhydrous and oxygen-free condition is meant that the content of water and oxygen in the system continues less than 10ppm.And load type non-metallocene catalyst of the present invention is in that the pressure-fired preservation is subsequent use down in airtight nitrogen envelope usually after the preparation.
In one embodiment, the invention still further relates to the magnesium compound load type non-metallocene catalyst of making by the preparation method of aforementioned load type non-metallocene catalyst.
The magnesium compound load type non-metallocene catalyst that the present invention makes constitutes catalystsystem jointly with promotor, can be used for the homopolymerization/copolymerization of catalyzed alkene.
Through being Primary Catalysts with magnesium compound load type non-metallocene catalyst of the present invention; To be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more is promotor, homopolymerization and/or copolymerization that can catalyzed alkene.
Homopolymerization and/or copolymerization process to said alkene do not have special qualification, can adopt well known in the art those, such as enumerating slurry process, emulsion method, solution method, substance law and vapor phase process.
Said alkene is selected from C 2～C 10Monoolefine, diolefin, cycloolefin and other ethylenically unsaturated compounds.Particularly, said C 2～C 10Monoolefine can be enumerated ethene, propylene, 1-butylene, 1-hexene, 1-heptene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-hendecene, 1-laurylene, 1-cyclopentenes, norbornylene, norbornadiene and vinylbenzene; Said diolefin can enumerate 1; 4-divinyl, 2,5-pentadiene, 1,6-hexadiene and 1; The 7-octadiene, and said other ethylenically unsaturated compounds can be enumerated vinyl acetate and (methyl) propenoate.Need be pointed out that here that the said homopolymerization of the present invention is meant a kind of polymerization of alkene, and copolymerization is meant the polymerization between the two or more alkene.
As previously mentioned, said promotor can be 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 aikyiaiurnirsoxan beta and aluminum alkyls, those that mentioned when conduct helps chemical processing agent before can adopting, wherein preferable methyl aikyiaiurnirsoxan beta and triethyl aluminum.
Preparing method's technology simple possible of magnesium compound load type non-metallocene catalyst of the present invention, and the charge capacity of Nonmetallocene part is adjustable, can improve its charge capacity significantly, improves the polymerization activity of this catalyzer thus significantly.
In addition, through adopting different chemical processing agent consumptions, can obtain polymerization activity from low to high and adjustable load type non-metallocene catalyst adapts to different olefin polymerization requirement thus.
When employing load type non-metallocene catalyst that the present invention obtained and promotor constitute catalystsystem, only need fewer promotor (such as MAO or triethyl aluminum) consumption, just can obtain high olefin polymerizating activity.
Embodiment
Below adopt embodiment that the present invention is described in further detail, but the invention is not restricted to these embodiment.
Polymer stacks density measurement reference standard GB 1636-79 carries out that (unit is g/cm 3).
The content of magnesium and titanium adopts ICP-AES to measure in the magnesium compound load type non-metallocene catalyst.
The polymerization activity of catalyzer calculates according to following method: after polyreaction finishes; Polymerisate in the reaction kettle is filtered and drying; The quality of this polymerisate of weighing then representes that divided by the ratio of the quality of used load type non-metallocene catalyst (unit is a kg polymkeric substance/gCat) for the polymerization activity of catalyzer with this polymerisate quality.
Embodiment 1
Magnesium compound is Magnesium Chloride Anhydrous (MgCl 2), chemical processing agent is titanium tetrachloride (TiCl 4).
Take by weighing the 5g Magnesium Chloride Anhydrous, preparation makes its dispersion with solvent as product of contact to add the 25ml hexane, then under agitation with being added dropwise to titanium tetrachloride in 30 minutes; React 4 hours after-filtration down at 60 ℃; Hexane wash 3 times, each 25ml, vacuum is drained and is obtained product of contact.Titanium tetrachloride and magnesium compound mole proportioning are 1: 2.
The Nonmetallocene part of structural formula
Figure S2007101626760D00391
is dissolved in (the part mass concentration is 100 grams per liters) in the hexane; Under agitation add product of contact then; React 4 hours after-filtration; Hexane wash 2 times; Each hexane consumption 25ml descended dry 6 hours at 25 ℃ then, obtained magnesium compound load type non-metallocene catalyst.
Wherein part and product of contact quality proportioning are 0.11: 1.
This catalyzer is designated as CAT-1, and wherein Mg content is 13.7wt%, and titanium content is 8.4wt%.
Embodiment 1-1
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into magnesium bromide (MgBr 2), chemical processing agent is titanium tetrabromide (TiBr 4), the mole proportioning of itself and magnesium compound is 1: 4.5.
The product of contact preparation is changed into decane with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00401
and is dissolved in the decane part matter
Amount concentration is 50 grams per liters, and part and product of contact quality proportioning are 0.22: 1.
Embodiment 1-2
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC 2H 5)), chemical processing agent is changed into zirconium tetrachloride (ZrCl 4) (toluene solution), the mole proportioning of itself and magnesium compound is 1: 1.
The product of contact preparation is changed into toluene with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00402
and is dissolved in the toluene; The part mass concentration is 170 grams per liters, and part and product of contact quality proportioning are 0.29: 1.
Embodiment 1-3
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into butoxy magnesium bromide (MgBr (OC 4H 9)), chemical processing agent is changed into tetrabormated zirconium (ZrBr 4), the mole proportioning of itself and magnesium compound is 1: 30.
The product of contact preparation is changed into pentane with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00411
and is dissolved in the pentane; The part mass concentration is 90 grams per liters; Part and product of contact quality proportioning are 0.48: 1
Embodiment 1-4
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into magnesium ethylate (Mg (OC 2H 5) 2), chemical processing agent is changed into tetraethyl-titanium (Ti (CH 3CH 2) 4), the mole proportioning of itself and magnesium compound is 1: 25.
The product of contact preparation is changed into methylene dichloride with solvent.
The Nonmetallocene part is changed into and is dissolved in the methylene dichloride; The part mass concentration is 214 grams per liters, and part and product of contact quality proportioning are 0.15: 1.
React the back without filtration, direct 25 ℃ of following vacuum-dryings.
Embodiment 1-5
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into isobutoxy magnesium (Mg (i-OC 4H 9) 2), chemical processing agent is changed into tetrabutyl titanium (Ti (C 4H 9) 4), the mole proportioning of itself and magnesium compound is 1: 7.5.
The product of contact preparation is changed into YLENE with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00413
and is dissolved in the YLENE.
Embodiment 1-6
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into magnesium ethide (Mg (C 2H 5) 2), chemical processing agent is changed into tributyl titanium chloride (TiCl (C 4H 9) 3), the mole proportioning of itself and magnesium compound is 1: 20.
The product of contact preparation is changed into hexanaphthene with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00421
and is dissolved in the hexanaphthene.
Embodiment 1-7
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into isobutyl-magnesium (Mg (i-C 4H 9) 2), chemical processing agent is changed into four isobutoxy titanium (Ti (i-C 4H 9) 4).
The product of contact preparation is changed into methylcyclohexane with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00422
and is dissolved in the methylcyclohexane.
Embodiment 1-8
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into ethylmagnesium chloride (Mg (C 2H 5) Cl), chemical processing agent is changed into three isobutoxy ethyl zirconium (Zr (CH 3CH 2) (i-C 4H 9) 3).
The product of contact preparation is changed into chloro-hexane with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00423
and is dissolved in the chloro-hexane.
Embodiment 1-9
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into butylmagnesium chloride (Mg (C 4H 9) Cl), chemical processing agent is changed into diethoxy titanium dichloride (TiCl 2(OCH 3CH 2) 2).
The product of contact preparation is changed into chlorotoluene with solvent.
The Nonmetallocene part is changed into and is dissolved in the chlorotoluene.
Embodiment 1-10
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into butyl magnesium ethylate (Mg (OC 2H 5) (C 4H 9)).
The Nonmetallocene part is changed into
Figure S2007101626760D00432
Embodiment 1-11
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into magnesium chloride (MgCl 2) and magnesium ethylate (Mg (OC 2H 5) 2) mixture, both mol ratios are 1: 2.
The Nonmetallocene part is changed into
Figure S2007101626760D00433
Embodiment 1-12
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into magnesium ethylate (Mg (OC 2H 5) 2) and dibutyl magnesium (Mg (C 4H 9) 2) mixture, both mol ratios are 0.5: 1.
The Nonmetallocene part is changed into
Figure S2007101626760D00441
Embodiment 1-13
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into magnesium chloride (MgCl 2) and magnesium bromide (MgBr 2) mixture, both mol ratios are 1: 4.
The Nonmetallocene part is changed into
Embodiment 1-14
Basic identical with embodiment 1, but following change is arranged:
Magnesium compound is changed into oxyethyl group magnesium chloride (Mg (OC 2H 5) Cl) and ethyl butoxy magnesium (Mg (C 2H 5) (OC 4H 9)) mixture, both mol ratios are 0.5: 1.
The Nonmetallocene part is changed into
Figure S2007101626760D00443
Reference example 1-1
Basic identical with embodiment 1, but following change is arranged:
The quality proportioning of part and product of contact is 0.30: 1.
Catalyzer is designated as CAT-A.Wherein Mg content is 12.3wt%, and titanium content is 7.9wt%.
Can know that by this reference example it is identical that product of contact prepares process, but the content of magnesium and titanium reduces in the load type non-metallocene catalyst.This phenomenon is because the increase of Nonmetallocene part add-on causes the charge capacity of load type non-metallocene catalyst due to increasing.The preparation method of magnesium compound load type non-metallocene catalyst of the present invention is adopted in this explanation, can obtain high Nonmetallocene part charge capacity, and its charge capacity is adjustable.
Reference example 1-2
Basic identical with embodiment 1, but following change is arranged:
The mole proportioning of titanium tetrachloride and magnesium compound is 1: 1.
Catalyzer is designated as CAT-B.Wherein Mg content is 11.6wt%, and titanium content is 9.7wt%.
Under the identical condition of Nonmetallocene part add-on; Increasing this phenomenon by titanium content increase in the load type non-metallocene catalyst and Mg content reduction, polymerization activity can know; Adopt the preparation method of magnesium compound load type non-metallocene catalyst of the present invention; Can pass through to adopt different chemical processing agent consumptions, and obtain the active high load type non-metallocene catalyst of catalysis in olefine polymerization.
Embodiment 2
Hereinafter; For the event of simplicity of exposition; With chemical processing agent with help the combination of chemical processing agent to be referred to as the composite chemical treatment agent, and be the consumption that benchmark confirms to help chemical processing agent with the chemical processing agent, but this with the present invention before specialized range produce contradiction.
Magnesium compound is a Magnesium Chloride Anhydrous, and the composite chemical treatment agent is titanium tetrachloride and triethyl aluminum.
Take by weighing the 5g Magnesium Chloride Anhydrous, add the 25ml hexane and disperse, then under agitation with the hexane solution that was added dropwise to triethyl aluminum in 15 minutes; React 1 hour after-filtration, hexane wash 1 time obtains prefinished products; Again to wherein under agitation with dripping titanium tetrachloride in 30 minutes, at 60 ℃ of reaction 2h after-filtration down, with hexane wash 3 times; Each hexane consumption 25ml, 25 ℃ of dryings made product of contact after 6 hours.
Wherein, titanium tetrachloride and magnesium mole proportioning are 1: 2, with the triethyl aluminum mol ratio be 1: 1.
The Nonmetallocene part of structural formula
Figure S2007101626760D00461
is dissolved in (the part mass concentration is 100 grams per liters) in the hexane; Under agitation add product of contact then; React 4 hours after-filtration; Hexane wash 2 times; Each hexane consumption 25ml, 25 ℃ were descended dry 6 hours then, obtained magnesium compound load type non-metallocene catalyst.
Wherein part and product of contact quality proportioning are 0.11: 1.
Catalyzer is designated as CAT-2.
Embodiment 2-1
Basic identical with embodiment 2, but following change is arranged:
Magnesium compound is changed into magnesium bromide (MgBr 2), the composite chemical treatment agent is titanium tetrachloride-MAO, titanium tetrachloride and magnesium compound mol ratio are 1: 4.5, with the MAO mol ratio be 1: 2.
Under agitation with the toluene solution that was added dropwise to MAO in 15 minutes, react 2 hours after-filtration earlier, toluene wash 1 time under agitation dripped titanium tetrachloride with 30 minutes again, reacted 0.5h after-filtration, toluene wash 2 times down at 105 ℃.
The Nonmetallocene part is changed into
Figure S2007101626760D00462
and is dissolved in the toluene.
The part mass concentration is 50 grams per liters, and part and product of contact quality proportioning are 0.22: 1.
Embodiment 2-2
Basic identical with embodiment 2, but following change is arranged:
Magnesium compound is changed into oxyethyl group magnesium chloride (MgCl (OC 2H 5)), the composite chemical treatment agent is zirconium tetrachloride (ZrCl 4)-triethyl aluminum, zirconium tetrachloride and triethyl aluminum mol ratio are 1: 0.5, with the mole proportioning of magnesium compound be 1: 1.
Under agitation with the n-heptane solution that was added dropwise to triethyl aluminum in 15 minutes, react 2 hours after-filtration earlier, heptane wash 2 times more under agitation with the toluene solution that dripped zirconium tetrachloride in 30 minutes, is reacted 4h after-filtration, heptane wash 1 time down at 100 ℃.
The Nonmetallocene part is changed into
Figure S2007101626760D00471
and is dissolved in the heptane.
The part mass concentration is 170 grams per liters, and part and product of contact quality proportioning are 0.29: 1.
Embodiment 2-3
Basic identical with embodiment 2, but following change is arranged:
The composite chemical treatment agent is titanium tetrabromide (TiBr 4)-triethyl aluminum, titanium tetrabromide and triethyl aluminum mol ratio are 1: 0.25.
Under agitation with the decane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 1 hour earlier,, react the 1h after-filtration down at 110 ℃, decane washing 1 time more under agitation with the decane solution that dripped titanium tetrabromide in 30 minutes.
The Nonmetallocene part is changed into
Figure S2007101626760D00472
and is dissolved in the decane.
The part mass concentration is 79 grams per liters, and part and product of contact quality proportioning are 0.48: 1.
Embodiment 2-4
Basic identical with embodiment 2, but following change is arranged:
The composite chemical treatment agent is tetrabormated zirconium (ZrBr 4)-triisobutyl aluminium, tetrabormated zirconium and triisobutyl al mole ratio are 1: 2.
Under agitation with the pentane solution that was added dropwise to triisobutyl aluminium in 15 minutes, react after 1 hour earlier,, react the 8h after-filtration down at 30 ℃, the pentane washing more under agitation with the pentane solution that dripped the tetrabormated zirconium in 30 minutes.
The Nonmetallocene part is changed into
Figure S2007101626760D00481
and is dissolved in the methylene dichloride.
The part mass concentration is 214 grams per liters, and part and product of contact quality proportioning are 0.15: 1.Directly vacuum is drained.
Embodiment 2-5
Basic identical with embodiment 2, but following change is arranged:
Magnesium compound is changed into magnesium ethylate.
The composite chemical treatment agent is titanium tetrachloride-trimethylaluminium, and titanium tetrachloride and trimethylaluminium mol ratio are 1: 4.The ethylbenzene washing.
The Nonmetallocene part is changed into
Figure S2007101626760D00482
and is dissolved in the ethylbenzene.
Embodiment 2-6
Basic identical with embodiment 2, but following change is arranged:
Magnesium compound is changed into isobutoxy magnesium (Mg (i-OC 4H 9) 2).
The composite chemical treatment agent is titanium tetrachloride-aluminum ethylate, and titanium tetrachloride and triethoxy al mole ratio are 1: 1, with the mole proportioning of magnesium compound be 1: 7.5.
The Nonmetallocene part is changed into and is dissolved in the hexanaphthene.
Embodiment 2-7
Basic identical with embodiment 2, but following change is arranged:
Magnesium compound is changed into ethylmagnesium chloride (Mg (C 2H 5) Cl).
The composite chemical treatment agent is titanium tetrachloride-triisobutyl alumina alkane, and triisobutyl alumina alkane and titanium tetrachloride mol ratio are 1: 1.
The Nonmetallocene part is changed into
Figure S2007101626760D00491
and is dissolved in the methylcyclohexane.
Embodiment 2-8
Basic identical with embodiment 2, but following change is arranged:
Magnesium compound is changed into butyl magnesium ethylate (Mg (OC 2H 5) (C 4H 9)).
The Nonmetallocene part is changed into
Embodiment 2-9
Basic identical with embodiment 2, but following change is arranged:
Magnesium compound is changed into butylmagnesium chloride (Mg (C 4H 9) Cl).
The Nonmetallocene part is changed into
Figure S2007101626760D00493
Embodiment 2-10
Basic identical with embodiment 2, but following change is arranged:
Magnesium compound is changed into magnesium chloride (MgCl 2) and magnesium ethylate (Mg (OC 2H 5) 2) mixture, both mol ratios are 1: 2.
The Nonmetallocene part is changed into
Figure S2007101626760D00501
Embodiment 2-11
Basic identical with embodiment 2, but following change is arranged:
Magnesium compound is changed into magnesium ethylate (Mg (OC 2H 5) 2) and dibutyl magnesium (Mg (C 4H 9) 2) mixture, both mol ratios are 0.5: 1.
The Nonmetallocene part is changed into
Embodiment 3
Magnesium compound is a Magnesium Chloride Anhydrous, and chemical processing agent is a titanium tetrachloride.
The 5g Magnesium Chloride Anhydrous is dissolved in THF and the alcohol mixed solution, is heated to 60 ℃, stirring reaction formed solution after 1.5 hours; Add the 25ml hexane then and make the magnesium compound deposition; Filter then, 25ml hexane wash 1 time, heating under vacuum to 80 ℃ are drained and to be made the modification magnesium compound.
In gained modification magnesium compound, add the 50ml hexane, under agitation be added dropwise to titanium tetrachloride with 30 minutes, reacted 4 hours down at 60 ℃, filter, adopt hexane wash 3 times, each hexane consumption 25ml was heated to 90 ℃ of dryings 2 hours then, obtained product of contact.
The Nonmetallocene part of structural formula
Figure S2007101626760D00503
is dissolved in the hexane; Under agitation add product of contact then; React 4 hours after-filtration; Adopt hexane wash 2 times; Each hexane consumption 25ml, 25 ℃ were descended dry 2 hours then, obtained magnesium compound load type non-metallocene catalyst.
Wherein, The mol ratio of Magnesium Chloride Anhydrous and THF is 1: 12, with the alcoholic acid mol ratio be 1: 4, the mole proportioning of magnesium is 1: 2 in titanium tetrachloride and the modification magnesium compound; The part mass concentration is 100 grams per liters, and part and product of contact quality proportioning are 0.11: 1.
This catalyzer is designated as CAT-3.
Embodiment 3-1
Basic identical with embodiment 3, but following change is arranged:
Magnesium chloride changes magnesium bromide (MgBr into 2), with the mol ratio of THF be 1: 20.
Ethanol changes propyl alcohol into, and the mol ratio of magnesium bromide and propyl alcohol is 1: 3.
Chemical processing agent is changed into titanium tetrabromide (TiBr 4), with the mole proportioning of magnesium in the modification magnesium compound be 1: 4.5.
Adopt decane to make the magnesium compound deposition, and with decane washing 2 times.
The Nonmetallocene part is changed into
Figure S2007101626760D00511
and is dissolved in the decane.
The part mass concentration is 50 grams per liters, and part and product of contact quality proportioning are 0.22: 1.
Embodiment 3-2
Basic identical with embodiment 3, but following change is arranged:
Magnesium chloride changes oxyethyl group magnesium chloride (MgCl (OC into 2H 5)), with the mol ratio of THF be 1: 20.
Ethanol changes butanols into, and the mol ratio of oxyethyl group magnesium chloride and butanols is 1: 6.
Chemical processing agent is changed into (ZrCl 4), at first being dissolved in the toluene, the mole proportioning of magnesium is 1: 1 in zirconium tetrachloride and the modification magnesium compound.
Adopt pentane to make the magnesium compound deposition, and with pentane washing 3 times.
The Nonmetallocene part is changed into
Figure S2007101626760D00521
and is dissolved in the toluene.
The part mass concentration is 170 grams per liters, and part and product of contact quality proportioning are 0.29: 1.
Embodiment 3-3
Basic identical with embodiment 3, but following change is arranged:
Magnesium chloride changes butoxy magnesium bromide (MgBr (OC into 4H 9)), ethanol changes hexanol into.
The mol ratio of butoxy magnesium bromide and THF is 1: 14, with the mol ratio of hexanol be 1: 15,
Chemical processing agent is changed into tetrabormated zirconium (ZrBr 4), with the mole proportioning of magnesium in the modification magnesium compound be 1: 30.
Adopt hexanaphthene to make the magnesium compound deposition, and wash with hexanaphthene.
The Nonmetallocene part is changed into and is dissolved in the hexanaphthene.
The part mass concentration is 79 grams per liters, and part and product of contact quality proportioning are 0.48: 1.
Embodiment 3-4
Basic identical with embodiment 3, but following change is arranged:
Magnesium chloride changes magnesium ethylate (Mg (OC into 2H 5) 2), the mol ratio of magnesium ethylate and THF is 1: 10.
Ethanol changes enanthol into, and the mol ratio of butoxy magnesium chloride and enanthol is 1: 6.3,
Chemical processing agent is changed into tetraethyl-titanium (Ti (CH 3CH 2) 4), with the mole proportioning of magnesium in the modification magnesium compound be 1: 25.
The product of contact preparation is changed into methylene dichloride with solvent.
The Nonmetallocene part is changed into and is dissolved in the methylene dichloride.
The part mass concentration is 214 grams per liters, and part and product of contact quality proportioning are 0.15: 1.Without filtration, direct 25 ℃ of following vacuum-dryings.
Embodiment 3-5
Basic identical with embodiment 3, but following change is arranged:
Magnesium chloride changes isobutoxy magnesium (Mg (i-OC into 4H 9) 2), the mol ratio of isobutoxy magnesium and THF is 1: 25.
Ethanol changes hexalin into.
Chemical processing agent is changed into (Ti (C 4H 9) 4), with the mole proportioning of magnesium in the modification magnesium compound be 1: 7.5.
The product of contact preparation is changed into YLENE with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00532
and is dissolved in the YLENE.
Embodiment 3-6
Basic identical with embodiment 3, but following change is arranged:
Magnesium compound is changed into magnesium ethide (Mg (C 2H 5) 2), ethanol changes the phenyl butanols into;
Chemical processing agent is changed into tributyl titanium chloride (TiCl (C 4H 9) 3), magnesium mole proportioning is 1: 20 in tributyl titanium chloride and the modification magnesium compound;
Adopt hexanaphthene to make the magnesium compound deposition, and wash with hexanaphthene.
The Nonmetallocene part is changed into
Figure S2007101626760D00541
dissolving Nonmetallocene part
Solvent is changed into hexanaphthene.
Embodiment 3-7
Basic identical with embodiment 3, but following change is arranged:
Magnesium compound is changed into isobutyl-magnesium (Mg (i-C 4H 9) 2), chemical processing agent is changed into four isobutoxy titanium (Ti (i-C 4H 9) 4).
The product of contact preparation is changed into methylcyclohexane with solvent.
The Nonmetallocene part is changed into and is dissolved in the methylcyclohexane.
Embodiment 3-8
Basic identical with embodiment 3, but following change is arranged:
Magnesium compound is changed into ethylmagnesium chloride (Mg (C 2H 5) Cl), chemical processing agent is changed into three isobutoxy ethyl zirconium (Zr (CH 3CH 2) (i-C 4H 9) 3).
The product of contact preparation is changed into chloro-hexane with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00543
and is dissolved in the chloro-hexane.
Embodiment 4
Magnesium compound is a Magnesium Chloride Anhydrous, and the composite chemical treatment agent is titanium tetrachloride and triethyl aluminum.
The 5g Magnesium Chloride Anhydrous is added in THF and the alcohol mixed solvent, under agitation be heated to 60 ℃, form solution after 1.5 hours; Add the 25ml hexane then and make the magnesium compound deposition; Filter then, 25ml hexane wash 1 time, heating under vacuum to 80 ℃ are drained and to be made the modification magnesium compound.
In this modification magnesium compound under agitation with the hexane solution that was added dropwise to triethyl aluminum in 15 minutes (concentration is 0.88mol/L); React after 1 hour; Under agitation dripped titanium tetrachloride again, react 2h after-filtration, hexane wash 3 times down at 60 ℃ with 30 minutes; Each hexane consumption 25ml, 25 ℃ of dryings made product of contact in back 6 hours.
Nonmetallocene part with structural formula
Figure S2007101626760D00551
; Be dissolved in the hexane; Under agitation add above-mentioned product of contact then, reacted 4 hours, filter; Hexane wash 2 times; Each hexane consumption 25ml, 25 ℃ were descended dry 6 hours then, obtained magnesium compound load type non-metallocene catalyst.
Wherein, the mol ratio of magnesium chloride and THF is 1: 12, with the alcoholic acid mol ratio be 1: 4, titanium tetrachloride and triethyl aluminum mol ratio are 1: 1 in the composite chemical treatment agent, with the mole proportioning of magnesium in the modification magnesium compound be 1: 2.
The part mass concentration is 100 grams per liters, and part and product of contact quality proportioning are 0.11: 1.
This catalyzer is designated as CAT-4.
Embodiment 4-1
Basic identical with embodiment 4, but following change is arranged:
Magnesium chloride changes magnesium bromide (MgBr into 2), ethanol changes propyl alcohol into.
Adopt decane to make the magnesium compound deposition, and with decane washing 2 times.
The composite chemical treatment agent is titanium tetrachloride-MAO.Under agitation with the toluene solution that was added dropwise to MAO in 15 minutes (concentration is 10wt%), react after 4 hours earlier, filter, under agitation dripped titanium tetrachloride again, react the 0.5h after-filtration down at 105 ℃, decane washing 2 times with 30 minutes.
Wherein, the mol ratio of magnesium bromide and THF is 1: 20, with the mol ratio of propyl alcohol be 1: 3, titanium tetrachloride with the MAO mol ratio be 1: 2, with the mole proportioning of magnesium in the modification magnesium compound be 1: 4.5.
The Nonmetallocene part is changed into
Figure S2007101626760D00561
and is dissolved in the decane.
The part mass concentration is 50 grams per liters, and part and product of contact quality proportioning are 0.22: 1.
Embodiment 4-2
Basic identical with embodiment 4, but following change is arranged:
Magnesium chloride changes oxyethyl group magnesium chloride (MgCl (OC into 2H 5)), ethanol changes butanols into.
The mol ratio of oxyethyl group magnesium chloride and THF is 1: 20, with the mol ratio of butanols be 1: 6.
The composite chemical treatment agent is zirconium tetrachloride (ZrCl 4)-triethyl aluminum, zirconium tetrachloride and triethyl aluminum mol ratio are 1: 0.5, with the mole proportioning of magnesium in the modification magnesium compound be 1: 1.
Wherein, earlier under agitation with the toluene solution that was added dropwise to triethyl aluminum in 15 minutes, react 2 hours after-filtration, toluene wash 1 time more under agitation with the toluene solution that dripped zirconium tetrachloride in 30 minutes, is reacted 4h after-filtration, toluene wash down at 100 ℃.
The Nonmetallocene part is changed into
Figure S2007101626760D00562
and is dissolved in the toluene.
The part mass concentration is 170 grams per liters, and part and product of contact quality proportioning are 0.29: 1.
Embodiment 4-3
Basic identical with embodiment 4, but following change is arranged:
Magnesium chloride changes butoxy magnesium bromide (MgBr (OC into 4H 9)), ethanol changes hexanol into.
The mol ratio of butoxy magnesium bromide and THF is 1: 14, with the mol ratio of hexanol be 1: 15,
Adopt hexanaphthene to make the magnesium compound deposition, and wash with hexanaphthene.
The composite chemical treatment agent is titanium tetrabromide (TiBr 4)-triethyl aluminum, titanium tetrabromide and triethyl aluminum mol ratio are 1: 0.25, with the mole proportioning of magnesium in the modification magnesium compound be 1: 34.
Earlier under agitation with the decane solution that was added dropwise to triethyl aluminum in 15 minutes, react after 1 hour more under agitation with the decane solution that dripped titanium tetrabromide in 30 minutes, under 110 ℃, react the 1h after-filtration, decane washs 4 times.
The Nonmetallocene part is changed into
Figure S2007101626760D00571
and is dissolved in the decane.
The part mass concentration is 79 grams per liters, and part and product of contact quality proportioning are 0.48: 1.
Embodiment 4-4
Basic identical with embodiment 4, but following change is arranged:
Magnesium chloride changes magnesium ethylate (Mg (OC into 2H 5) 2), ethanol changes enanthol into.
The mol ratio of magnesium ethylate and THF is 1: 10, with the mol ratio of enanthol be 1: 6.3,
The composite chemical treatment agent is titanium tetrachloride-trimethylaluminium, and titanium tetrachloride and trimethylaluminium mol ratio are 1: 4.
Under agitation be added dropwise to earlier the pentane solution of triethyl aluminum, react after 1 hour,, react 8h after-filtration, washed with dichloromethane down at 30 ℃ more under agitation with the pentane solution that dripped the tetrabormated zirconium in 30 minutes with 15 clocks.
The Nonmetallocene part is changed into
Figure S2007101626760D00572
and is dissolved in the methylene dichloride.
The part mass concentration is 214 grams per liters, and part and product of contact quality proportioning are 0.15: 1.Without filtration, direct 25 ℃ of following vacuum-dryings.
Embodiment 4-5
Basic identical with embodiment 4, but following change is arranged:
Magnesium chloride changes isobutoxy magnesium (Mg (i-OC into 4H 9) 2), with the mol ratio of THF be 1: 25.
Ethanol changes hexalin into.
The composite chemical treatment agent is tetrabormated zirconium-triisobutyl aluminium, and tetrabormated zirconium and triisobutyl al mole ratio are 1: 4.Earlier under agitation be added dropwise to triisobutyl aluminium, react after 1 hour,, react the 8h after-filtration down at 50 ℃, the YLENE washing more under agitation with the xylene solution that dripped the tetrabormated zirconium in 30 minutes with 15 minutes.
The Nonmetallocene part is changed into
Figure S2007101626760D00581
and is dissolved in the YLENE.
Embodiment 4-6
Basic identical with embodiment 4, but following change is arranged:
Magnesium compound is changed into magnesium ethide (Mg (C 2H 5) 2), ethanol changes the phenyl butanols into;
Adopt hexanaphthene to make the magnesium compound deposition, and wash with hexanaphthene.
The composite chemical treatment agent is titanium tetrachloride-aluminum ethylate, and titanium tetrachloride and triethyl aluminum mol ratio are 1: 1.
The Nonmetallocene part is changed into
Figure S2007101626760D00582
and is dissolved in the hexanaphthene.
Embodiment 4-7
Basic identical with embodiment 4, but following change is arranged:
Magnesium compound is changed into isobutyl-magnesium (Mg (i-C 4H 9) 2).
The composite chemical treatment agent is titanium tetrachloride-triisobutyl alumina alkane, and titanium tetrachloride and triisobutyl alumina alkane mol ratio are 1: 1.
The Nonmetallocene part is changed into
Figure S2007101626760D00591
and is dissolved in the methylcyclohexane.
Embodiment 4-8
Basic identical with embodiment 4, but following change is arranged:
Magnesium compound is changed into ethylmagnesium chloride (Mg (C 2H 5) Cl).
The product of contact preparation is changed into chloro-hexane with solvent.
The Nonmetallocene part is changed into
Figure S2007101626760D00592
and is dissolved in the chloro-hexane.
Embodiment 5 (application implementation example)
CAT-A that makes in the catalyzer CAT-1, CAT-2, CAT-3, CAT-4 and the reference example that make in the embodiment of the invention and CAT-B are adopted slurry polymerization processes respectively in 2 liters of polymerization autoclaves; With the hexane is polymer solvent; With MAO or triethyl aluminum is promotor; Be to make ethylene homo under 2 hours the condition in stagnation pressure 0.8MPa, 85 ℃ of polymerization temperatures, hydrogen partial pressure 0.2MPa and reaction times; Research changes promotor consumption (aluminium titanium mol ratio) and plants time-like, and to the polymerization activity of catalyzer and the influence of polymer stacks density, the result is as shown in table 1.
The olefinic polyreaction effect of table 1. magnesium compound load type non-metallocene catalyst
Sequence number The catalyzer numbering Promotor Aluminium titanium mol ratio Polymerization activity (kgPE/gCat) Polymer stacks density (g/cm 3)
1 CAT-1 Triethyl aluminum 90 4.34 0.274
2 CAT-1 Triethyl aluminum 500 4.47 0.275
3 CAT-1 MAO 140 4.81 0.292
4 CAT-1 MAO 500 4.93 0.294
5 CAT-A Triethyl aluminum 90 4.77 0.277
6 CAT-B Triethyl aluminum 90 6.42 0.313
7 CAT-2 Triethyl aluminum 90 6.79 0.334
8 CAT-2 MAO 140 7.21 0.342
9 CAT-3 Triethyl aluminum 90 13.40 0.365
10 CAT-3 MAO 140 14.16 0.350
11 CAT-4 Triethyl aluminum 90 15.93 0.352
12 CAT-4 MAO 140 16.83 0.333
Contrast through sequence number in the table 11 and 2,3 and 4 test-results data can be known, increases the consumption of promotor triethyl aluminum, and when promptly improving aluminium titanium mol ratio, influence active to polymerization catalyst and polymer stacks density is not remarkable.Can explain thus, adopt the magnesium compound load type non-metallocene catalyst of method preparation provided by the invention only to need fewer promotor consumption just can obtain high olefin polymerizating activity.
The contrast of the test-results data through sequence number in the table 11 and 5 and 6 can be known, through improving chemical processing agent consumption or Nonmetallocene part add-on, can improve the polymerization activity of the catalyzer of gained, and improve the bulk density of polymkeric substance.Can explain that thus adopt the magnesium compound load type non-metallocene catalyst of method preparation provided by the invention, its polymerization activity is adjustable flexibly, therefore can be adapted to different olefin polymerization requirement widely.
In addition, can know that the kind influence active to polymerization catalyst and polymer stacks density that changes promotor is not remarkable through the contrast of sequence number in the table 17 and 8,9 and 10,11 and 12 test-results data.Can explain thus, adopt the magnesium compound load type non-metallocene catalyst of method preparation provided by the invention, have bigger latitude at the kind time-like of selecting promotor.

Claims (36)

1. the preparation method of a magnesium compound load type non-metallocene catalyst, it may further comprise the steps:
Magnesium compound is contacted with the chemical processing agent that is selected from IVB family metallic compound, obtain product of contact step and
Handle said product of contact with the Nonmetallocene part, obtain the step of said load type non-metallocene catalyst.
2. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 1; Also be included in before said chemical processing agent contacts, handle the step of said magnesium compound with the chemical processing agent that helps that is selected from aikyiaiurnirsoxan beta, aluminum alkyls and its mixture.
3. according to the preparation method of claim 1 or 2 described magnesium compound load type non-metallocene catalysts, it is characterized in that said magnesium compound is through modification.
4. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 3; It is characterized in that said modification magnesium compound is to make it to precipitate with solvent and obtain through in by said magnesium compound and solution that THF-pure mixed solvent constitutes, adding deposition.
5. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 1, it is characterized in that, also comprise through filtering and washing, perhaps without filtration and washing, and the step of the load type non-metallocene catalyst that convection drying obtained.
6. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 1, it is characterized in that said treatment step carries out in the presence of the solvent of the said Nonmetallocene part of solubilized.
7. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 6; It is characterized in that the solvent of the said Nonmetallocene part of said solubilized is selected from one or more in alkane, naphthenic hydrocarbon, halogenated alkane, halo naphthenic hydrocarbon, aromatic hydrocarbon and the halogenated aromatic.
8. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 7, it is characterized in that the solvent of the said Nonmetallocene part of said solubilized is selected from one or more in alkane, halogenated alkane and the aromatic hydrocarbon.
9. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 8, it is characterized in that the solvent of the said Nonmetallocene part of said solubilized is selected from one or more in hexane, methylene dichloride and the toluene.
10. according to the preparation method of the described magnesium compound load type non-metallocene catalyst of claim 1; It is characterized in that said magnesium compound is selected from one or more in magnesium halide, alkoxyl group magnesium halide, alkoxyl magnesium, alkyl magnesium, alkyl halide magnesium and the alkyl alkoxy magnesium.
11. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 10 is characterized in that, said magnesium compound is selected from magnesium halide, oxyethyl group magnesium halide, magnesium ethylate and butoxy magnesium.
12. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, said IVB family metallic compound is selected from one or more in halogenide, alkylate and the halogenated alkyl compounds of IVB family metal.
13. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 12 is characterized in that, said IVB family metallic compound is selected from IVB family metal halide.
14. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 13 is characterized in that, said IVB family metal halide is selected from titanium tetrachloride and zirconium tetrachloride.
15. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, is 1: 0.1～100 in the said chemical processing agent of IVB family metallic element with mol ratio in the said magnesium compound of magnesium elements.
16. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 15 is characterized in that, is 1: 0.5～50 in the said chemical processing agent of IVB family metallic element with mol ratio in the said magnesium compound of magnesium elements.
17. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, the mass ratio of said Nonmetallocene part and said product of contact is 0.01～0.50: 1.
18. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 17 is characterized in that, the mass ratio of said Nonmetallocene part and said product of contact is 0.10～0.30: 1.
19. preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 4; It is characterized in that; Said alcohol is selected from one or more in Fatty Alcohol(C12-C14 and C12-C18), aromatic alcohol and the alicyclic ring alcohol, and the optional group that is selected from alkyl, halogen atom and alkoxyl group of wherein said alcohol replaces.
20. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 19 is characterized in that, said alcohol is selected from Fatty Alcohol(C12-C14 and C12-C18).
21. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 20 is characterized in that, said Fatty Alcohol(C12-C14 and C12-C18) is selected from ethanol and butanols.
22. preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 4; It is characterized in that; In the said magnesium compound of magnesium elements and the mol ratio of THF is 1: 5～100, is 1: 0.5～20 in the said magnesium compound of magnesium elements and the mol ratio of said alcohol.
23. preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 22; It is characterized in that; In the said magnesium compound of magnesium elements and the mol ratio of THF is 1: 10～30, is 1: 1～8 in the said magnesium compound of magnesium elements and the mol ratio of said alcohol.
24. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 4 is characterized in that, by volume, it is 1: 0.5～6 that said deposition is used the solvent and the ratio of THF.
25. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 24 is characterized in that, by volume, it is 1: 1～4 that said deposition is used the solvent and the ratio of THF.
26. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 4 is characterized in that, said deposition is selected from alkane with solvent.
27. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 26 is characterized in that, said deposition is selected from pentane, hexane, heptane and decane with solvent.
28. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 2 is characterized in that, the said chemical processing agent that helps is selected from MAO, isobutyl aluminium alkoxide, triethyl aluminum and the triisobutyl aluminium one or more.
29. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 2 is characterized in that, is 1: 0.5～8 in the said magnesium compound of magnesium elements with helping the mol ratio of chemical processing agent in aluminium element said.
30. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 29 is characterized in that, is 1: 1～4 in the said magnesium compound of magnesium elements with helping the mol ratio of chemical processing agent in aluminium element said.
31. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 1 is characterized in that, said Nonmetallocene part is selected from the compound with following structure:
Wherein:
Q is selected from 0 or 1;
D is selected from 0 or 1;
A be selected from Sauerstoffatom, sulphur atom, selenium atom,
Figure FSB00000696293800042
-NR 23R 24,-N (O) R 25R 26,
Figure FSB00000696293800043
-PR 28R 29,-P (O) R 30OR 31, sulfuryl, sulfoxide group or-Se (O) R 39
B is selected from nitrogen-containing group, phosphorus-containing groups or C 1-C 30Alkyl;
D is selected from Sauerstoffatom, sulphur atom, selenium atom, nitrogenous C 1-C 30Alkyl, phosphorated C 1-C 30Alkyl, sulfuryl, sulfoxide group,
Figure FSB00000696293800044
-N (O) R 25R 26,
Figure FSB00000696293800045
Or-P (O) R 32(OR 33), wherein N, O, S, Se, P are respectively ligating atom;
E is selected from nitrogen-containing group, oxy radical, sulfur-containing group, contains seleno group or phosphorus-containing groups, and wherein N, O, S, Se, P are respectively ligating atom;
G is selected from C 1-C 30Alkyl, substituted C 1-C 30Alkyl or safing function property group;
→ represent singly-bound or two key;
-represent covalent linkage or ionic linkage;
R 1, R 2, R 3, R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, R 30, R 31, R 32, R 33And R 39Be selected from hydrogen, C independently of one another 1-C 30Alkyl, halogen atom, substituted C 1-C 30Alkyl or safing function property group, above-mentioned group can be the same or different to each other, and wherein adjacent group can become key or Cheng Huan each other, and
Said safing function property group is selected from halogen, oxy radical, nitrogen-containing group, silicon-containing group, germanic group, sulfur-containing group or contains tin group.
32. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 31 is characterized in that,
Said halogen is selected from F, Cl, Br, I;
Said nitrogen-containing group is selected from
Figure FSB00000696293800051
-NR 23R 24,-T-NR 23R 24Or-N (O) R 25R 26
Said phosphorus-containing groups is selected from
Figure FSB00000696293800052
-PR 28R 29,-P (O) R 30R 31,-P (O) R 32(OR 33) ,-T-PR 28(OR 29) ,-T-P (O) R 30R 31Or-T-P (O) R 32(OR 33);
Said oxy radical be selected from hydroxyl ,-OR 34With-T-OR 34
Said sulfur-containing group is selected from-SR 35,-T-SR 35,-S (O) R 36Or-T-SO 2R 37
The said seleno group that contains is selected from-SeR 38,-T-SeR 38,-T-Se (O) R 39Or-Se (O) R 39
Said group T is selected from C 1-C 30Alkyl or substituted C 1-C 30Alkyl;
Said C 1-C 30Alkyl is selected from C 1-C 30Alkyl, C 2-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;
Said substituted C 1-C 30Alkyl is selected from halogenated C 1-C 30Alkyl, halogenated C 6-C 30Aryl, halogenated C 8-C 30Condensed ring radical or halogenated C 4-C 30Heterocyclic radical;
Said silicon-containing group is selected from-SiR 42R 43R 44,-T-SiR 45
Said germanic group is selected from-GeR 46R 47R 48,-T-GeR 49
Saidly contain tin group and be selected from-SnR 50R 51R 52,-T-SnR 53Or-T-Sn (O) R 54
Said R 34, R 35, R 36, R 37, R 38And R 42, R 43, R 44, R 45, R 46, R 47, R 48, R 49, R 50, R 51, R 52, R 53, R 54Be selected from hydrogen, C independently of one another 1-C 30Alkyl, halogen atom or substituted C 1-C 30Alkyl.
33. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 31 is characterized in that,
Said Nonmetallocene part is selected from the compound with following structure:
Figure FSB00000696293800053
Figure FSB00000696293800061
34. the preparation method according to the described magnesium compound load type non-metallocene catalyst of claim 33 is characterized in that,
Said Nonmetallocene part is selected from the compound with following structure:
Figure FSB00000696293800062
35. magnesium compound load type non-metallocene catalyst; Comprise carrier and load non-metallocene catalyst on it; It is characterized in that it is to make according to the preparation method of each described magnesium compound load type non-metallocene catalyst of claim 1～34.
36. the homopolymerization of an alkene and/or copolymerization process; Magnesium compound load type non-metallocene catalyst with claim 35 is a Primary Catalysts, is promotor to be selected from aikyiaiurnirsoxan beta, aluminum alkyls, haloalkyl aluminium, boron fluothane, boron alkyl and the boron alkyl ammonium salt one or more.
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